JP5156578B2 - Polyethylene-based laminating material and laminated body thereof - Google Patents
Polyethylene-based laminating material and laminated body thereof Download PDFInfo
- Publication number
- JP5156578B2 JP5156578B2 JP2008278175A JP2008278175A JP5156578B2 JP 5156578 B2 JP5156578 B2 JP 5156578B2 JP 2008278175 A JP2008278175 A JP 2008278175A JP 2008278175 A JP2008278175 A JP 2008278175A JP 5156578 B2 JP5156578 B2 JP 5156578B2
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- polar group
- layered silicate
- laminating material
- molded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000573 polyethylene Polymers 0.000 title claims description 137
- -1 Polyethylene Polymers 0.000 title claims description 130
- 239000004698 Polyethylene Substances 0.000 title claims description 111
- 239000000463 material Substances 0.000 title claims description 57
- 238000010030 laminating Methods 0.000 title claims description 38
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 62
- 239000000178 monomer Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 229910052618 mica group Inorganic materials 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 20
- 239000010445 mica Substances 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 230000035699 permeability Effects 0.000 claims description 10
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 5
- 239000002648 laminated material Substances 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 description 49
- 239000007789 gas Substances 0.000 description 40
- 238000000034 method Methods 0.000 description 31
- 230000000694 effects Effects 0.000 description 29
- 238000006116 polymerization reaction Methods 0.000 description 24
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 20
- 230000000704 physical effect Effects 0.000 description 20
- 229920005672 polyolefin resin Polymers 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000000465 moulding Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002667 nucleating agent Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000805 composite resin Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- VBZMQBCINSHBFF-PLNGDYQASA-N 1-o-butyl 4-o-(oxiran-2-ylmethyl) (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCC1CO1 VBZMQBCINSHBFF-PLNGDYQASA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OALMZWNBNXQUAL-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide Chemical compound NC(=O)C(C)(C)N=NC(C)(C)C(N)=O OALMZWNBNXQUAL-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- JNWRGTDFPPYRAD-UHFFFAOYSA-N 2-ethylhexan-1-amine;hydron;chloride Chemical compound Cl.CCCCC(CC)CN JNWRGTDFPPYRAD-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- UKQJZQQPMIFNHE-UHFFFAOYSA-N 2-isocyanatoprop-1-ene Chemical compound CC(=C)N=C=O UKQJZQQPMIFNHE-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- JGBFIXUYGYOXMY-ONEGZZNKSA-N 4-o-(oxiran-2-ylmethyl) 1-o-propyl (e)-but-2-enedioate Chemical compound CCCOC(=O)\C=C\C(=O)OCC1CO1 JGBFIXUYGYOXMY-ONEGZZNKSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JGBFIXUYGYOXMY-UHFFFAOYSA-N C(C=C/C(=O)OCC1CO1)(=O)OCCC Chemical compound C(C=C/C(=O)OCC1CO1)(=O)OCCC JGBFIXUYGYOXMY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VJLOFJZWUDZJBX-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;chloride Chemical compound [Cl-].OCC[NH2+]CCO VJLOFJZWUDZJBX-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000021185 dessert Nutrition 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- NDMVEPBCXVVMEN-UHFFFAOYSA-N dibenzyl(dioctadecyl)azanium Chemical class C=1C=CC=CC=1C[N+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CC1=CC=CC=C1 NDMVEPBCXVVMEN-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 235000020124 milk-based beverage Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical class CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000269 smectite group Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、ポリエチレン系積層用材料及びその積層体に関するもので、より詳しくは、有機化層状珪酸塩を極性基含有ポリエチレン中に分散させた組成物を用いて成形され、ガスバリア性、成形性に優れ、かつ透明性に優れた、ポリエチレン系積層用材料、さらには、空気中の酸素等によって悪影響を受けないガスバリア性を有したインモールドラベル容器など、各種包装容器分野等で広く利用できる積層体に関するものである。 The present invention relates to a polyethylene-based laminating material and a laminate thereof. More specifically, the present invention is molded using a composition in which an organically modified layered silicate is dispersed in a polar group-containing polyethylene, thereby improving gas barrier properties and moldability. Laminate that can be widely used in various packaging container fields such as polyethylene-based laminating materials with excellent transparency, and in-mold label containers with gas barrier properties that are not adversely affected by oxygen in the air. It is about.
合成樹脂の射出成形等によって一体成形された容器は、乳飲料やビール等の飲み物用容器や、乾燥食品容器、さらには、カット果物やフルーツゼリー等のデザート食品用容器として、種々のものが提案されている。このような容器は、その収容すべき飲み物や食品によって、空気中の酸素等によって悪影響を受けない十分なガスバリア性が求められる。
一方、インモールドラベル成形といって、ブローや射出成形時に金型にあらかじめヒートシール層をもつラベルをセットしておき、成形時の樹脂のもつ熱でラベルのヒートシール層を成形品表面に融着させることにより、成形と同時にラベリングを行なう方法があるが、ガスバリア性のラベルを用いない場合、樹脂自体にガスバリア性を持たせる必要がある。しかも、ラベルの文字を判読できるようにするため、成形樹脂自体の透明性が高いことが要求される。
従来、ポリオレフィン系樹脂の分野において、ガスバリア性を改良するために、ポリオレフィン系樹脂にバリア性樹脂を積層した成形品やポリオレフィン系樹脂にバリア性樹脂を分散させた成形品等が広く使用されている。
一方、層状珪酸塩などの層状無機化合物をポリオレフィン系樹脂に分散させ、ガスバリア性等の物性を改良する試みが従来から数多く行なわれている。（例えば、特許文献１〜６参照）
また、透明性（ヘイズ）に関しては、ポリオレフィン系樹脂の分野において、造核剤等の添加剤、異種の樹脂を添加するといった試みがなされている。（例えば、特許文献７〜９参照）
Various containers have been proposed that are integrally molded by injection molding of synthetic resin, such as drink containers for milk beverages and beer, dry food containers, and dessert food containers such as cut fruits and fruit jelly. Has been. Such a container is required to have sufficient gas barrier properties that are not adversely affected by oxygen in the air or the like depending on the drink or food to be stored.
On the other hand, in-mold label molding, a label with a heat seal layer is set in advance in the mold during blow or injection molding, and the heat seal layer of the label is melted onto the surface of the molded product by the heat of the resin during molding. Although there is a method of labeling at the same time as molding, if the gas barrier label is not used, the resin itself needs to have gas barrier property. Moreover, it is required that the molding resin itself has high transparency so that the characters on the label can be read.
Conventionally, in the field of polyolefin resins, in order to improve gas barrier properties, molded products in which barrier resins are laminated on polyolefin resins, molded products in which barrier resins are dispersed in polyolefin resins, and the like have been widely used. .
On the other hand, many attempts have been made in the past to improve physical properties such as gas barrier properties by dispersing a layered inorganic compound such as layered silicate in a polyolefin resin. (For example, see Patent Documents 1 to 6)
In addition, with regard to transparency (haze), attempts have been made to add additives such as nucleating agents and different types of resins in the field of polyolefin resins. (For example, see Patent Documents 7 to 9)
特開平１０−２９８３５８号公報（特許文献１）には、ポリオレフィン樹脂５０ないし９９．９重量％、層状珪酸塩０．１ないし５０重量％とからなる組成物を主成分とし、かつ成形体の酸素透過係数と成形体を構成する組成物の主成分であるポリオレフィン樹脂の酸素透過係数および層状珪酸塩の体積分率との間に特定の関係式が成立するガスバリア性樹脂成形体が提案されている。
しかしながら、その場合、ガスバリア性向上効果としては必ずしも満足できるものではなく、また、成形性、成形品外観、機械的強度等の諸特性について好適な成形品が得られるわけではない。
Japanese Patent Laid-Open No. 10-298358 (Patent Document 1) discloses a composition comprising 50 to 99.9% by weight of a polyolefin resin and 0.1 to 50% by weight of a layered silicate as a main component, and oxygen in the molded body. There has been proposed a gas barrier resin molded body in which a specific relational expression is established between the permeability coefficient and the oxygen transmission coefficient of the polyolefin resin, which is the main component of the composition constituting the molded body, and the volume fraction of the layered silicate. .
However, in this case, the effect of improving the gas barrier property is not always satisfactory, and a molded product suitable for various properties such as moldability, molded product appearance, and mechanical strength cannot be obtained.
また、特開２０００−３５５６４０号公報（特許文献２）には、ポリオレフィン系樹脂１００重量部及び有機化層状珪酸塩０．１〜５０重量部からなるポリオレフィン系樹脂複合材料であって、前記有機化層状珪酸塩が、結晶構造中に交換性カチオンとして含有する金属イオンがカチオン系界面活性剤にてイオン交換された有機化層状珪酸塩であり、且つ該有機化層状珪酸塩の結晶側面の水酸基が、水酸基との化学結合性もしくは化学親和性を有する官能基を分子の末端に有する化学物質にて化学修飾されて成るポリオレフィン系樹脂複合材料が提案されている。 JP 2000-355640 A (Patent Document 2) discloses a polyolefin resin composite material comprising 100 parts by weight of a polyolefin resin and 0.1 to 50 parts by weight of an organic layered silicate, The layered silicate is an organized layered silicate in which metal ions contained as exchangeable cations in the crystal structure are ion-exchanged with a cationic surfactant, and the hydroxyl group on the crystal side surface of the organized layered silicate has A polyolefin-based resin composite material that has been chemically modified with a chemical substance having a functional group having chemical bondability or chemical affinity with a hydroxyl group at the end of the molecule has been proposed.
また、特開２００１−０６４４５４号公報（特許文献３）には、ポリオレフィン系樹脂１００重量部及び有機化層状珪酸塩０．１〜５０重量部からなるポリオレフィン系樹脂複合材料において、該有機化層状珪酸塩が、結晶構造中に交換性カチオンとして含有する金属イオンがカチオン系界面活性剤にてイオン交換された有機化層状珪酸塩であり、且つ該有機化層状珪酸塩の結晶側面が、アニオン性界面活性能を有する化合物にて化学修飾されて成るポリオレフィン系樹脂複合材料が提案されている。 Japanese Patent Laid-Open No. 2001-064454 (Patent Document 3) discloses a polyolefin resin composite material comprising 100 parts by weight of a polyolefin resin and 0.1 to 50 parts by weight of an organic layered silicate, and the organic layered silicic acid. The salt is an organic layered silicate in which a metal ion contained as an exchangeable cation in the crystal structure is ion-exchanged with a cationic surfactant, and the crystal side surface of the organic layered silicate has an anionic interface A polyolefin-based resin composite material that has been chemically modified with a compound having an activity ability has been proposed.
また、特開２００３−１０５２００号公報（特許文献４）には、樹脂１００重量部及び層状珪酸塩０．１〜２０重量部を含有する樹脂組成物であって、前記層状珪酸塩は、層状結晶の少なくとも一部の単層同士が単層表面の中心をずらせて重なりあって、見掛け上、厚さ５〜５０ｎｍ、長さ５００ｎｍ以上の平板状となって分散している樹脂組成物が提案されている。
しかしながら、これらの材料の場合、ある程度のガスバリア性向上効果を発揮するものの、成形性、成形品外観、機械的強度等の諸特性について必ずしも満足できる成形品が得られるわけではない。
Japanese Patent Application Laid-Open No. 2003-105200 (Patent Document 4) discloses a resin composition containing 100 parts by weight of resin and 0.1 to 20 parts by weight of layered silicate, wherein the layered silicate includes layered crystals. A resin composition is proposed in which at least some of the monolayers overlap with each other by shifting the center of the monolayer surface, and apparently are dispersed in the form of a flat plate having a thickness of 5 to 50 nm and a length of 500 nm or more. ing.
However, in the case of these materials, although a gas barrier property improving effect is exhibited to some extent, a molded product that is satisfactory in terms of various properties such as moldability, appearance of the molded product, and mechanical strength is not necessarily obtained.
また、特開２００４−０９１７７５号公報（特許文献５）には、オレフィン系重合体、極性官能基を分子内に含有する有機カチオンにより有機化された層状無機化合物、および当該オレフィン重合体と相容性を有し、極性官能基を分子内に有する極性重合体、からなるオレフィン系重合体であって、当該組成物中の当該有機化された層状無機化合物の層間距離が２０オングストローム以上であるオレフィン系重合体組成物が提案されている。
しかしながら、この場合も、ある程度のガスバリア性向上効果を発揮するものの、成形性、成形品外観、機械的強度等の諸特性について必ずしも満足できる成形品が得られるわけではない。
JP-A-2004-091775 (Patent Document 5) discloses an olefin polymer, a layered inorganic compound organized by an organic cation containing a polar functional group in the molecule, and compatibility with the olefin polymer. An olefin polymer comprising a polar polymer having a polar functional group in its molecule, wherein the interlayer distance of the organically layered inorganic compound in the composition is 20 angstroms or more System polymer compositions have been proposed.
However, in this case as well, although a gas barrier property improving effect is exhibited to some extent, it is not always possible to obtain a molded product that satisfies various properties such as moldability, appearance of the molded product, and mechanical strength.
更に、特開２００６−１３１８９６号公報（特許文献６）には、層間に有機物がインターカレートされた層状珪酸塩と、側鎖に極性基を有する変性オレフィン系重合体とを混合して得られた組成物であって、Ｘ線回折スペクトル上に、層状珪酸塩の底面間隔に相当するピークを有さないことを特徴とする変性オレフィン系重合体組成物が提案されている。
しかしながら、この場合、分散性の改良については改善効果が開示されているものの、ガスバリア性、成形性等の諸特性について必ずしも満足できる成形品が得られるわけではない。加えて、実際に製品として使用した場合、十分な衝撃強度を保持出来ない場合がある。
Further, JP-A-2006-131896 (Patent Document 6) is obtained by mixing a layered silicate in which an organic substance is intercalated between layers and a modified olefin polymer having a polar group in a side chain. A modified olefin polymer composition characterized by not having a peak corresponding to the interval between the bottom surfaces of the layered silicate on the X-ray diffraction spectrum has been proposed.
However, in this case, although an improvement effect is disclosed for improving the dispersibility, a molded product that is satisfactory for various properties such as gas barrier properties and moldability is not always obtained. In addition, when actually used as a product, sufficient impact strength may not be maintained.
一方、特開平１０−１３９９９８号公報（特許文献７）には、ポリフェニレンエーテル及びポリオレフィン中に層状珪酸塩を分散させた密閉型蓄電池ケーシング材料であって、成形性、機械的強度、耐熱性のバラスに優れ、かつ水蒸気バリア性に優れた組成物が提案されている。
しかしながら、この場合、成形品の透明性はある程度達成できるものの、バリア性の対象は水蒸気であり、水蒸気バリア性が向上しても、必ずしも酸素ガスのバリア性が向上するものではない。また、曲げ弾性率の改良効果は必ずしも大きいものではない。
On the other hand, Japanese Patent Laid-Open No. 10-139998 (Patent Document 7) discloses a sealed storage battery casing material in which layered silicate is dispersed in polyphenylene ether and polyolefin, and has a moldability, mechanical strength, and heat resistance ballast. In addition, a composition excellent in water vapor barrier properties has been proposed.
However, in this case, although transparency of the molded product can be achieved to some extent, the target of the barrier property is water vapor, and even if the water vapor barrier property is improved, the barrier property of oxygen gas is not necessarily improved. Further, the effect of improving the flexural modulus is not necessarily great.
また、特開２００６−０８９５５８号公報（特許文献８）には、酸素、水蒸気の進入を防止することで金属からの剥離を防止するため、ポリオレフィン系樹脂に層状無機物、極性官能基含有オレフィン系オリゴマー、ゴム状弾性体を含む酸素、水蒸気のバリア性を有した金属被覆用ポリオレフィン系樹脂組成物が提案されている。
しかしながら、この場合、ある程度の透明性とある程度のガスバリア性向上効果を発揮するものの、必ずしも満足できるガスバリア性を有した成形品が得られるわけではない。
In addition, JP 2006-089558 A (Patent Document 8) discloses that a layered inorganic substance and a polar functional group-containing olefin oligomer are added to a polyolefin resin in order to prevent exfoliation from the metal by preventing oxygen and water vapor from entering. In addition, a polyolefin resin composition for metal coating having a barrier property against oxygen and water vapor containing a rubber-like elastic body has been proposed.
However, in this case, although a certain degree of transparency and a certain degree of gas barrier property improving effect are exhibited, a molded product having a satisfactory gas barrier property is not necessarily obtained.
また、特開２０００−３１９４０７号公報（特許文献９）には、ポリオレフィン樹脂に造核剤を添加することにより、透明性がよく、ＥＳＣＲも良好なインサート成形体が提案されている。
しかしながら、この場合、ある程度のヘイズ向上効果が発揮されるものの、必ずしも満足できるものではなく、また、ガスバリア性はヘイズが向上しても必ずしも向上するものではない。
Japanese Patent Application Laid-Open No. 2000-319407 (Patent Document 9) proposes an insert molded body having good transparency and good ESCR by adding a nucleating agent to a polyolefin resin.
However, in this case, although a certain degree of haze improvement effect is exhibited, it is not always satisfactory, and the gas barrier property is not necessarily improved even if the haze is improved.
本発明の目的は、上記問題点を解決し、ガスバリア性の向上効果のみならず、成形性、成形品外観、機械的強度の改良に加えて、透明性、特にヘイズの低減効果に優れたポリエチレン系積層用材料、及び空気中の酸素等によって悪影響を受けないガスバリア性を有したカップ状のインモールド容器などの積層体を提供することにある。 The object of the present invention is to solve the above-mentioned problems and not only improve the gas barrier properties but also improve the moldability, the appearance of the molded product and the mechanical strength, as well as the transparency, especially the haze reduction effect. An object of the present invention is to provide a laminated body such as a cup-shaped in-mold container having a gas barrier property that is not adversely affected by oxygen-based laminating material and oxygen in the air.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、結晶の球晶サイズを微細にしてヘイズ低減させる従来技術とは異なり、特定のポリエチレンを使用し、特定の粘度特性を有する積層用材料が、結晶中に層状無機化合物を取り込んで結晶化度を低下させることができ、また、溶融分子鎖の絡み合い緩和を促進させ、流動性を向上でき、これを用いることにより、ガスバリア性を有したカップ状のインモールド容器などの積層体を容易に得ることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have used a specific polyethylene and a specific viscosity characteristic, unlike the conventional technique in which the spherulite size of the crystal is reduced to reduce haze. The laminating material has a layered inorganic compound incorporated into the crystal to reduce the crystallinity, promotes the entanglement of the molten molecular chain, improves the fluidity, and uses this to provide a gas barrier. It has been found that a laminated body such as a cup-shaped in-mold container having the property can be easily obtained, and the present invention has been completed.
すなわち、本発明の第１の発明によれば、有機化層状珪酸塩（Ａ）５〜３０重量％と、密度が０．９４０〜０．９７０ｇ／ｃｍ３、温度１９０℃、荷重２．１６ｋｇにて測定されるメルトフローレート（ＭＦＲ）が３〜３５ｇ／１０分である極性基含有ポリエチレン（Ｂ）７０〜９５重量％とからなるポリエチレン系積層用材料であって、
極性基含有ポリエチレン（Ｂ）は、前駆体としての極性基を含まないエチレン系重合体に極性基としてカルボン酸無水物基を有するエチレン性不飽和単量体をグラフト反応させた重合体、又はこれに極性基を含まないエチレン系重合体をブレンドした重合体であり、かつ下記の特性（１）〜（４）を満足することを特徴とするポリエチレン系積層用材料が提供される。
特性（１）：キャピラリーレオメーターにて温度１９０℃、せん断速度４８ｓｅｃ−１で測定される粘度η４８（Ｐａ・ｓ）とせん断速度３１００ｓｅｃ−１で測定される粘度η３１００（Ｐａ・ｓ）の比（η４８／η３１００）が７〜３０である。
特性（２）：ポリエチレン系積層用材料を成形したときの酸素透過係数Ｐ（ｃｍ３・ｍｍ／ｍ２・２４ｈｒ・ａｔｍ）（２３℃・６５％ＲＨ）と、ポリエチレン系積層用材料の主成分である極性基含有ポリエチレン（Ｂ）の酸素透過係数Ｐ０（ｃｍ３・ｍｍ／ｍ２・２４ｈｒ・ａｔｍ）（２３℃・６５％ＲＨ）の比Ｐ／Ｐ０が０．７以下である。
特性（３）：成形したときの曲げ弾性率が９００ＭＰａ以上である。
特性（４）：ポリエチレン系積層用材料を成形したときのヘイズτ（％）が８０％以下であり、かつポリエチレン系積層用材料の主成分である極性基含有ポリエチレン（Ｂ）のヘイズτ０（％）との比τ／τ０が０．８以下である。
That is, according to the first invention of the present invention, the organic layered silicate (A) is 5 to 30% by weight, the density is 0.940 to 0.970 g / cm 3 , the temperature is 190 ° C., and the load is 2.16 kg. melt flow rate is measured Te (MFR) is a polyethylene laminated material comprising a polar group-containing polyethylene (B) 70 to 95% by weight is 3 to 35 g / 10 min,
The polar group-containing polyethylene (B) is a polymer obtained by graft-reacting an ethylenically unsaturated monomer having a carboxylic acid anhydride group as a polar group to an ethylene polymer that does not contain a polar group as a precursor, or this There is provided a polyethylene-based laminating material characterized in that it is a polymer obtained by blending an ethylene-based polymer containing no polar group and satisfies the following characteristics (1) to (4).
Characteristic (1): Viscosity η 48 (Pa · s) measured at a temperature of 190 ° C. and a shear rate of 48 sec −1 with a capillary rheometer and a viscosity η 3100 (Pa · s) measured at a shear rate of 3100 sec −1 The ratio (η 48 / η 3100 ) is 7-30.
Characteristic (2): Oxygen transmission coefficient P (cm 3 · mm / m 2 · 24 hr · atm) (23 ° C. · 65% RH) when a polyethylene laminate material is molded, and main components of the polyethylene laminate material The ratio P / P 0 of the oxygen permeability coefficient P 0 (cm 3 · mm / m 2 · 24 hr · atm) (23 ° C. · 65% RH) of the polar group-containing polyethylene (B) is 0.7 or less.
Characteristic (3): The bending elastic modulus when molded is 900 MPa or more.
Characteristic (4): Haze τ (%) when the polyethylene-based laminating material is molded is 80% or less, and haze τ 0 of the polar group-containing polyethylene (B) which is the main component of the polyethylene-based laminating material. %) And the ratio τ / τ 0 is 0.8 or less.
また、本発明の第２の発明によれば、第１の発明において、有機化層状珪酸塩（Ａ）に用いられる層状珪酸塩が、モンモリロナイト及び／又はマイカであることを特徴とするポリエチレン系積層用材料が提供される。 According to the second invention of the present invention, in the first invention, the layered silicate used in the organically modified layered silicate (A) is montmorillonite and / or mica, Materials are provided.
また、本発明の第３の発明によれば、第１又は第２の発明において、さらに、極性基含有ポリエチレン（Ｂ）が、エチレン性不飽和単量体を０．１〜５．０重量％含むことを特徴とするポリエチレン系積層用材料が提供される。
According to the third invention of the present invention, in the first or second invention, the polar group-containing polyethylene (B) further comprises 0.1 to 5.0% by weight of an ethylenically unsaturated monomer. A polyethylene-based laminating material characterized by comprising is provided.
一方、本発明の第４の発明によれば、第１〜３のいずれかの発明に係り、前記ポリエチレン系積層用材料を用い、少なくとも基材と積層してなる積層体が提供される。 On the other hand, according to a fourth invention of the present invention, there is provided a laminate formed by laminating at least a base material using the polyethylene-based lamination material according to any one of the first to third inventions.
また、本発明の第５の発明によれば、第４の発明において、インモールドラベル容器として用いられることを特徴とする積層体が提供される。 Moreover, according to the 5th invention of this invention, in 4th invention, the laminated body characterized by being used as an in-mold label container is provided.
本発明によれば、ガスバリア性、特に酸素透過防止性に優れるばかりでなく、成形品外観、成形性等の諸特性に優れ、加えて耐衝撃性に優れたポリエチレン系積層用材料及びその成形体を得ることができる。
特に、ガスバリア性だけでなく、透明性に優れる（ヘイズが低く）という特性により、ガスバリア性インモールドラベル容器など各種包装分野をはじめ広範囲の分野で利用できるので、産業上の有用性は非常に高い。
According to the present invention, a polyethylene-based laminating material having excellent gas barrier properties, particularly oxygen permeation-preventing properties, as well as various properties such as appearance of a molded product and moldability, and also excellent impact resistance, and a molded product thereof Can be obtained.
In particular, because it has excellent transparency (low haze) as well as gas barrier properties, it can be used in a wide range of fields including gas barrier in-mold label containers, so it has very high industrial utility. .
以下に、本発明を詳細に説明する。
本発明のポリエチレン系積層用材料は、有機化層状珪酸塩（Ａ）５〜３０重量％と、密度が０．９４０〜０．９７０ｇ／ｃｍ３、温度１９０℃、荷重２．１６ｋｇにて測定されるメルトフローレート（ＭＦＲ）が３〜３５ｇ／１０分である極性基含有ポリエチレン（Ｂ）７０〜９５重量％とからなるポリエチレン系積層用材料であって、
極性基含有ポリエチレン（Ｂ）は、前駆体としての極性基を含まないエチレン系重合体に極性基としてカルボン酸無水物基を有するエチレン性不飽和単量体をグラフト反応させた重合体、又はこれに極性基を含まないエチレン系重合体をブレンドした重合体であり、かつ下記の特性（１）〜（４）を満足することを特徴とする。
以下、本発明のポリエチレン系積層用材料の（Ａ）成分、（Ｂ）成分、その他の任意成分や、その成形方法等について、項目別に詳細に説明する。
The present invention is described in detail below.
The polyethylene-based laminating material of the present invention is measured at 5 to 30% by weight of the organic layered silicate (A), a density of 0.940 to 0.970 g / cm 3 , a temperature of 190 ° C., and a load of 2.16 kg. A polyethylene-based laminating material comprising 70 to 95% by weight of a polar group-containing polyethylene (B) having a melt flow rate (MFR) of 3 to 35 g / 10 min,
The polar group-containing polyethylene (B) is a polymer obtained by graft-reacting an ethylenically unsaturated monomer having a carboxylic acid anhydride group as a polar group to an ethylene polymer that does not contain a polar group as a precursor, or this And a polymer obtained by blending an ethylene-based polymer not containing a polar group, and satisfying the following characteristics (1) to (4).
Hereinafter, the (A) component, the (B) component, other optional components, the molding method, and the like of the polyethylene-based laminating material of the present invention will be described in detail for each item.
１．有機化層状珪酸塩（Ａ）
本発明のポリエチレン系積層用材料を構成する有機化層状珪酸塩（Ａ）とは、層状珪酸塩を有機化したものである。
層状珪酸塩としては、層間に交換性陽イオンを有する従来公知の珪酸塩鉱物であって、通常、厚さが１ｎｍ程度、平均アスペクト比が２０〜２００程度の薄片状結晶がイオン結合によって凝集してなるものであり、具体的には、例えば、モンモリロナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト、ソーコナイト等のスメクタイト族、バーミキュライト等のバーミキュライト族、白雲母、金雲母、テニオライト等の雲母族、カオリナイト、デイッカナイト、ナクライト、ハイロサイト等のカオリナイト族、クリノクロア、シャモサイト、ニマイト、スドーアイト、クッケアイト、ドンバサイト等の緑泥石族、及び、アポフィライト、タルク、マイカ等のフィロ珪酸塩鉱物が挙げられる。これらの層状珪酸塩は、単独で用いてもよく、２種以上を併用して用いてもよい。
これらの層状珪酸塩の中で、モンモリロナイト及び／又はマイカがガスバリア性及び分散性の改良効果が大きいので好ましい。
1. Organized layered silicate (A)
The organically modified layered silicate (A) constituting the polyethylene-based laminating material of the present invention is obtained by organicizing a layered silicate.
The layered silicate is a conventionally known silicate mineral having an exchangeable cation between layers, and usually flaky crystals having a thickness of about 1 nm and an average aspect ratio of about 20 to 200 are aggregated by ionic bonds. Specifically, for example, smectite group such as montmorillonite, beidellite, nontronite, saponite, hectorite, saconite, vermiculite group such as vermiculite, mica group such as muscovite, phlogopite, teniolite, Examples include kaolinites such as kaolinite, daikanite, nacrite, and hyrosite, chlorite such as clinochlore, chamosite, nimitite, sudite, kukeite, and donbasite, and phyllosilicate minerals such as apophyllite, talc, and mica. . These layered silicates may be used alone or in combination of two or more.
Among these layered silicates, montmorillonite and / or mica are preferable because they have a large effect of improving gas barrier properties and dispersibility.
本発明において、有機化層状珪酸塩（Ａ）とは、前記層状珪酸塩の層間に有機物がインターカレートされたものであり、その有機物としては、双極子モーメントを持つものであれば特に限定されるものではないが、有機アンモニウム塩、有機ホスホニウム塩、有機スルホニウム塩等の有機オニウム塩が好ましい。それらの中で、層状珪酸塩の層間を十分に非極性若しくは低極性化できることから、炭素数８以上のアルキル鎖を有する有機オニウム塩が好ましく、中でも、アンモニウム塩、ホスホニウム塩が更に好ましく、アンモニウム塩が特に好ましい。そのアンモニウム塩としては、具体的には、例えば、トリオクチルアンモニウム塩、ラウリルトリメチルアンモニウム塩、ステアリルアンモニウム塩、ステアリルトリメチルアンモニウム塩、ジステアリルジメチルアンモニウム塩、ジステアリルジベンジルアンモニウム塩等が挙げられる。
具体的な化合物としては、メチル・タロー・ビス（２−ヒドロキシエチル）アンモニウムクロリド、ジメチル・ベンジル・水素化タローアンモニウムクロリド、ジメチル・水素化タロー・２−エチルヘキシルアンモニウムクロリド、メチル・ジ水素化タローアンモニウムクロリド、ジメチル・ジ水素化タローアンモニウムクロリド、トリオクチルメチルアンモニウムクロリド、アルキル・ビス（２−ヒドロキシエチル）アンモニウムクロリド、ポリオキシプロピレンメチルジエチルアンモニウムクロリド等が好ましいものとして挙げられる。
In the present invention, the organic layered silicate (A) is an organic material intercalated between the layers of the layered silicate, and the organic material is not particularly limited as long as it has a dipole moment. Although not intended, organic onium salts such as organic ammonium salts, organic phosphonium salts, and organic sulfonium salts are preferred. Among them, an organic onium salt having an alkyl chain having 8 or more carbon atoms is preferable because the interlayer of the layered silicate can be sufficiently nonpolar or low in polarity, and among them, an ammonium salt and a phosphonium salt are more preferable, and an ammonium salt Is particularly preferred. Specific examples of the ammonium salt include trioctyl ammonium salt, lauryl trimethyl ammonium salt, stearyl ammonium salt, stearyl trimethyl ammonium salt, distearyl dimethyl ammonium salt, and distearyl dibenzyl ammonium salt.
Specific compounds include methyl, tallow, bis (2-hydroxyethyl) ammonium chloride, dimethyl, benzyl, hydrogenated tallow ammonium chloride, dimethyl, hydrogenated tallow, 2-ethylhexylammonium chloride, methyl dihydrogenated tallow ammonium. Preferred examples include chloride, dimethyl / dihydrogenated tallow ammonium chloride, trioctylmethyl ammonium chloride, alkyl bis (2-hydroxyethyl) ammonium chloride, polyoxypropylene methyl diethyl ammonium chloride and the like.
前記層状珪酸塩が層間に有する前記有機物の割合は、２０〜７０重量％であるのが好ましく、２５〜４０重量％であるのが特に好ましい。有機物の割合が前記範囲未満では、層状珪酸塩の層間を十分に非極性若しくは低極性化することが困難となる傾向となり、一方、前記範囲超過では、有機物がインターカレートされた層状珪酸塩の使用量に対する層状珪酸塩の割合が低下するため、層状珪酸塩の初期の目的が十分に発現し難い傾向となる。 The proportion of the organic substance that the layered silicate has between the layers is preferably 20 to 70% by weight, and particularly preferably 25 to 40% by weight. If the ratio of the organic substance is less than the above range, it tends to be difficult to make the layer of the layered silicate sufficiently non-polar or low-polarity, while if it exceeds the above range, the organic substance is intercalated in the layered silicate. Since the ratio of the layered silicate to the amount used decreases, the initial purpose of the layered silicate tends not to be sufficiently expressed.
本発明において、有機化層状珪酸塩（Ａ）としては、層間に有機物がインターカレートされた層状珪酸塩として市販されているものを用いることもでき、又、有機物がインターカレートされていない層状珪酸塩に前記有機物を加え、イオン交換することによって層間に前記有機物がインターカレートされた層状珪酸塩として調製したものを用いることもできる。 In the present invention, as the organically modified layered silicate (A), a commercially available layered silicate having an organic substance intercalated between layers can be used, or a layered form in which the organic substance is not intercalated. It is also possible to use a layered silicate prepared by intercalating the organic material between layers by adding the organic material to the silicate and performing ion exchange.
２．極性基含有ポリエチレン（Ｂ）
本発明のポリエチレン系積層用材料において、極性基含有ポリエチレン（Ｂ）とは、前駆体としての極性基を含まないエチレン系重合体に極性基を有するエチレン性不飽和単量体をグラフト反応させた重合体、又はこれに極性基を含まないエチレン系重合体をブレンドした重合体をいう。
極性基を含まないエチレン系重合体をブレンドする好ましい割合は、前駆体としての極性基を含まないエチレン系重合体に極性基を有するエチレン性不飽和単量体をグラフト反応させた重合体、若しくはエチレンの重合時に極性基を有するエチレン性不飽和単量体を共存させて共重合させた重合体１００〜５重量％に対して、０〜９５重量％である。
極性基含有ポリエチレンの前駆体としてのエチレン系重合体としては、具体的には、例えば、エチレンの単独重合体、エチレンと、プロピレン、１−ブテン、３−メチル−１−ブテン、１−ペンテン、４−メチル−１−ペンテン、４，４−ジメチル−１−ペンテン、１−ヘキセン、４−メチル−１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン、１−オクタデセン等の炭素数２〜１８程度の他のα−オレフィン等との二元或いは三元の共重合体等、具体的には、例えば、分岐状低密度ポリエチレン、直鎖状高密度ポリエチレン等のエチレン単独重合体、エチレン−プロピレン共重合体、エチレン−１−ブテン共重合体、エチレン−プロピレン−１−ブテン共重合体、エチレン−４−メチル−１−ペンテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−１−ヘプテン共重合体、エチレン−１−オクテン共重合体等のエチレン系樹脂が挙げられ、これらのエチレン系重合体は２種以上が併用されていてもよい。
また、改質を目的とする場合、ジエンとの共重合も可能である。このとき使用されるジエン化合物の例としては、ブタジエン、１，４−ヘキサジエン、エチリデンノルボルネン、ジシクロペンタジエン等を挙げることができる。なお、重合の際のコモノマー含有率は、任意に選択することができるが、例えば、エチレンと炭素数３〜１２のα−オレフィンとの共重合の場合には、エチレン・α−オレフィン共重合体中のα−オレフィン含有量は０〜４０モル％、好ましくは０〜３０モル％である。
2. Polar group-containing polyethylene (B)
In the polyethylene-based laminating material of the present invention, the polar group-containing polyethylene (B) is obtained by graft-reacting an ethylenically unsaturated monomer having a polar group to an ethylene polymer not containing a polar group as a precursor. It refers to a polymer or a polymer obtained by blending an ethylene polymer not containing a polar group.
A preferred ratio of blending an ethylene polymer not containing a polar group is a polymer obtained by graft-reacting an ethylenically unsaturated monomer having a polar group to an ethylene polymer not containing a polar group as a precursor, or It is 0 to 95% by weight with respect to 100 to 5% by weight of the polymer copolymerized by coexisting an ethylenically unsaturated monomer having a polar group during the polymerization of ethylene.
Specific examples of the ethylene polymer as a precursor of the polar group-containing polyethylene include, for example, ethylene homopolymer, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, Carbon number 2 such as 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-octadecene A binary or ternary copolymer with about 18 to other α-olefins, specifically, for example, ethylene homopolymers such as branched low-density polyethylene and linear high-density polyethylene, ethylene -Propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-he Sen copolymers, ethylene-heptene copolymers, include ethylene-based resin of an ethylene-1-octene copolymers, these ethylene polymers are more than two may be used together.
Moreover, when it aims at modification | reformation, the copolymerization with diene is also possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like. The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content therein is 0 to 40 mol%, preferably 0 to 30 mol%.
これらのエチレン系重合体は、分子量が重量平均分子量で２，０００〜５００，０００であるのが好ましく、５，０００〜２００，０００であるのが更に好ましく、１０，０００〜１００，０００であるのが特に好ましい。 These ethylene polymers preferably have a weight average molecular weight of 2,000 to 500,000, more preferably 5,000 to 200,000, and 10,000 to 100,000. Is particularly preferred.
前記のエチレン系重合体の重合触媒は、チーグラー触媒、フィリップス触媒、メタロセン触媒等の各種触媒が用いられる。重合触媒は、水素がオレフィン重合の連鎖移動作用を示すような触媒であればいずれも使用することができる。
具体的には、固体触媒成分と有機金属化合物とからなり、水素がオレフィン重合の連鎖移動作用を示すようなスラリー法オレフィン重合に適する触媒であればいずれも使用することができる。好ましくは重合活性点が局在している不均一系触媒である。
上記固体触媒成分としては、遷移金属化合物を含有するオレフィン重合用の固体触媒として用いられるものであれば特に制限はない。遷移金属化合物としては、周期表第４族〜第１０族、好ましくは第４族〜第６族の元素の化合物を使用することができ、具体例としては、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｍｏ等の化合物が挙げられる。
As the polymerization catalyst for the ethylene polymer, various catalysts such as a Ziegler catalyst, a Phillips catalyst, and a metallocene catalyst are used. Any polymerization catalyst can be used as long as hydrogen exhibits a chain transfer action of olefin polymerization.
Specifically, any catalyst that is composed of a solid catalyst component and an organometallic compound and that is suitable for slurry-based olefin polymerization such that hydrogen exhibits a chain transfer action of olefin polymerization can be used. Preferred is a heterogeneous catalyst in which polymerization active sites are localized.
The solid catalyst component is not particularly limited as long as it is used as a solid catalyst for olefin polymerization containing a transition metal compound. As the transition metal compound, compounds of elements of Group 4 to Group 10 of the periodic table, preferably Group 4 to Group 6, can be used, and specific examples include Ti, Zr, Hf, V, Cr. And compounds such as Mo.
また、前記のエチレン系重合体の重合触媒として用いることができるメタロセン触媒とは、活性点が比較的単一な、いわゆるシングルサイト触媒と呼ばれる種類の触媒であり、代表的なものとして、遷移金属のメタロセン錯体、例えばジルコニウムやチタンのビスシクロペンタジエニル錯体に助触媒としてのメチルアルミノキサン等を反応させて得られる触媒が挙げられ、各種の錯体、助触媒、担体等を種々組み合わせた均一又は不均一触媒である。
メタロセン触媒としては、例えば、特開昭５８−１９３０９号、同５９−９５２９２号、同５９−２３０１１号、同６０−３５００６号、同６０−３５００７号、同６０−３５００８号、同６０−３５００９号、同６１−１３０３１４号、特開平３−１６３０８８号公報等で公知であるものが挙げられる。
The metallocene catalyst that can be used as a polymerization catalyst for the ethylene-based polymer is a type of catalyst called a so-called single site catalyst having a relatively single active site. Metallocene complexes, for example, a catalyst obtained by reacting zirconium or titanium biscyclopentadienyl complex with methylaluminoxane as a co-catalyst, and homogeneous or non-uniform combinations of various complexes, co-catalysts, supports, etc. It is a homogeneous catalyst.
Examples of the metallocene catalyst include JP-A-58-19309, 59-95292, 59-23011, 60-35006, 60-35007, 60-35008, and 60-35009. No. 61-130314 and JP-A-3-163088, and the like.
前記のポリエチレンは、気相重合法、溶液重合法、スラリー重合法などの製造プロセスにより製造することができる。エチレン系重合体の重合条件のうち重合温度としては、０〜３００℃の範囲から選択することができる。重合圧力は、大気圧〜約１００ｋｇ／ｃｍ２の範囲から選択することができる。実質的に酸素、水等を断った状態で、ヘキサン、ヘプタン等の脂肪族炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素等から選ばれる不活性炭化水素溶媒の存在下でエチレン及びα−オレフィンの重合を行うことにより製造することができる。 The polyethylene can be produced by a production process such as a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method. Among the polymerization conditions of the ethylene polymer, the polymerization temperature can be selected from the range of 0 to 300 ° C. The polymerization pressure can be selected from the range of atmospheric pressure to about 100 kg / cm 2 . It is selected from aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, etc. in a state where oxygen and water are substantially cut off. It can be produced by polymerizing ethylene and α-olefin in the presence of an inert hydrocarbon solvent.
上記重合において、重合器に供給される水素は、連鎖移動剤として消費され、生成するエチレン系重合体の平均分子量を決定するほか、一部は溶媒に溶解して重合器から排出される。溶媒中への水素の溶解度は、小さく、重合器内に大量の気相部が存在しない限り、触媒の重合活性点付近の水素濃度は低い。そのため、水素供給量を変化させれば、触媒の重合活性点における水素濃度が速やかに変化し、生成するエチレン系重合体の分子量は、短時間の間に水素供給量に追随して変化する。従って、短い周期で水素供給量を変化させれば、より均質な製品を製造することができる。また、水素供給量の変化の態様は、連続的に変化させるよりも不連続的に変化させる方が、分子量分布を広げる効果が得られるので、好ましい。
また、本発明に係るエチレン系重合体においては、水素供給量を変化させることが重要であるが、その他の重合条件、例えば重合温度、触媒供給量、エチレンなどのオレフィンの供給量、１−ブテンなどのコモノマーの供給量、溶媒の供給量等を、適宜に水素の変化と同時に又は別個に変化させることも重要である。
In the above polymerization, hydrogen supplied to the polymerization vessel is consumed as a chain transfer agent, determines the average molecular weight of the produced ethylene-based polymer, and partly dissolves in a solvent and is discharged from the polymerization vessel. The solubility of hydrogen in the solvent is small, and the hydrogen concentration near the polymerization active point of the catalyst is low unless a large amount of gas phase is present in the polymerization vessel. Therefore, if the hydrogen supply amount is changed, the hydrogen concentration at the polymerization active point of the catalyst changes rapidly, and the molecular weight of the produced ethylene polymer changes following the hydrogen supply amount in a short time. Therefore, a more homogeneous product can be produced by changing the hydrogen supply rate in a short cycle. Moreover, the aspect of changing the hydrogen supply amount is preferably changed discontinuously rather than continuously because the effect of broadening the molecular weight distribution can be obtained.
In the ethylene polymer according to the present invention, it is important to change the hydrogen supply amount, but other polymerization conditions such as polymerization temperature, catalyst supply amount, supply amount of olefin such as ethylene, 1-butene It is also important to change the supply amount of the comonomer and the like, the supply amount of the solvent, etc., simultaneously with the change of hydrogen or separately.
前記エチレン系重合体を極性基含有ポリエチレンとなすには、前記エチレン系重合体に極性基を有するエチレン性不飽和単量体をグラフト反応させる方法、及び前記エチレン系重合体の重合時に、極性基を有するエチレン性不飽和単量体を共存させて共重合させる方法等の慣用方法を採り得るが、特にエチレン系重合体に極性基を有するエチレン性不飽和単量体をグラフト反応させる方法が好ましい In order to make the ethylene polymer into a polar group-containing polyethylene, a method of grafting an ethylenically unsaturated monomer having a polar group to the ethylene polymer, and a polar group at the time of polymerization of the ethylene polymer Conventional methods such as a method of copolymerization in the presence of an ethylenically unsaturated monomer having a polar group can be employed, but a method of grafting an ethylenically unsaturated monomer having a polar group to an ethylene polymer is particularly preferable.
エチレン性不飽和単量体としては、具体的には、例えば、カルボキシル基を有するエチレン性不飽和単量体としては、（メタ）アクリル酸〔ここで、「（メタ）アクリル」とは、「アクリル」又は／及び「メタクリル」を意味するものとする。〕、クロトン酸、イソクロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸等が、又、カルボン酸無水物基を有するエチレン性不飽和単量体としては、無水マレイン酸、無水イタコン酸、無水シトラコン酸等が、又、カルボン酸エステル基を有するエチレン性不飽和単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート等が、又、水酸基を有するエチレン性不飽和単量体としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２，３−ジヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシメチル−３−ヒドロキシプロピル（メタ）アクリレート、２，２−ジヒドロキシメチル−３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等が、又、エポキシ基を有するエチレン性不飽和単量体としては、グリシジル（メタ）アクリレート、プロピルグリシジルマレエート、ブチルグリシジルマレエート、プロピルグリシジルフマレート、ブチルグリシジルフマレート等が、又、アミド基を有するエチレン性不飽和単量体としては、（メタ）アクリルアミド等が、又、ニトリル基を有するエチレン性不飽和単量体としては、（メタ）アクリロニトリル等が、又、アミノ基を有するエチレン性不飽和単量体としては、アミノエチル（メタ）アクリレート等が、又、イミド基を有するエチレン性不飽和単量体としては、マレイン酸イミド等が、又、イソシアネート基を有するエチレン性不飽和単量体としては、２−イソシアネートエチル（メタ）アクリレート、（メタ）アクリロイルイソシアネート、ビニルイソシアネート、イソプロペニルイソシアネート等が、又、アセチル基を有するエチレン性不飽和単量体としては、酢酸ビニル等が、それぞれ挙げられ、又、極性基としてのチオール基、エーテル基、チオエーテル基、スルホン基、ホスホン基、ニトロ基、ウレタン基、ハロゲン原子等については、公知の方法で、オレフィン系重合体の主鎖に直接に付加して変性することができる。
これらの中でも不飽和カルボン酸及び／又はその誘導体が好ましく、本発明では、カルボン酸無水物基を有するエチレン性不飽和単量体を用い、特に、無水マレイン酸及び／又はその無水物が、層状珪酸塩の分散性の点から好ましい。
Specifically, as the ethylenically unsaturated monomer, for example, as the ethylenically unsaturated monomer having a carboxyl group, (meth) acrylic acid [here, “(meth) acryl” means “ It means “acrylic” or / and “methacrylic”. ], Crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., and ethylenically unsaturated monomers having a carboxylic acid anhydride group include maleic anhydride, itaconic anhydride, anhydrous Citraconic acid and the like, and ethylenically unsaturated monomers having a carboxylic acid ester group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, As the ethylenically unsaturated monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxymethyl-3- Hydroxypropyl (meth) acrylate, 2,2-dihydroxymethyl-3- Droxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like, and as an ethylenically unsaturated monomer having an epoxy group, glycidyl (meth) acrylate, Propyl glycidyl maleate, butyl glycidyl maleate, propyl glycidyl fumarate, butyl glycidyl fumarate, etc., and ethylenically unsaturated monomers having an amide group include (meth) acrylamide, etc. Examples of the ethylenically unsaturated monomer include (meth) acrylonitrile, and examples of the ethylenically unsaturated monomer having an amino group include aminoethyl (meth) acrylate, and ethylene having an imide group. Examples of the unsaturated monomer include maleic imide and the like, Examples of the ethylenically unsaturated monomer having a socyanate group include 2-isocyanatoethyl (meth) acrylate, (meth) acryloyl isocyanate, vinyl isocyanate, isopropenyl isocyanate and the like, and an ethylenically unsaturated monomer having an acetyl group Examples of the body include vinyl acetate and the like, and the thiol group, ether group, thioether group, sulfone group, phosphone group, nitro group, urethane group, halogen atom and the like as polar groups are known methods. It can be modified by adding directly to the main chain of the olefin polymer.
Among these, unsaturated carboxylic acids and / or derivatives thereof are preferable. In the present invention, an ethylenically unsaturated monomer having a carboxylic acid anhydride group is used. In particular, maleic anhydride and / or an anhydride thereof are layered. It is preferable from the point of dispersibility of silicate.
前記極性基を有するエチレン性不飽和単量体のグラフト反応は、例えば、ラジカル発生剤の存在下に、エチレン系重合体の溶融状態で行う溶融グラフト法、及び、有機溶媒による溶液状態で行う溶液グラフト法の慣用のいずれであってもよいが、溶剤を使用しないで製造できるという点から、溶融グラフト法によるのが好ましい。 The graft reaction of the ethylenically unsaturated monomer having a polar group is, for example, a melt grafting method performed in a molten state of an ethylene polymer in the presence of a radical generator, and a solution performed in a solution state using an organic solvent. Any of the conventional grafting methods may be used, but the melt grafting method is preferred because it can be produced without using a solvent.
その際、用いられるラジカル発生剤としては、具体的には、例えば、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン等のジアルキルパーオキサイド類、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシピバレート、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシイソプロピルカーボネート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキシン−３等のパーオキシエステル類、３，５，５−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ベンゾイルパーオキサイド等のジアシルパーオキサイド類、ｔ−ブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、ジイソプロピルベンゼンヒドロパーオキサイド、２，５−ジメチル−２，５−ジ（ヒドロパーオキシ）ヘキサン等のヒドロパーオキサイド類、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド等のケトンパーオキサイド類等の有機過酸化物類、又は、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（イソブチルアミド）ジハライド、２，２’−アゾビス〔２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド〕、アゾジ−ｔ−ブタン等のアゾ化合物類等が挙げられる。 In this case, specific examples of the radical generator used include di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di ( Dialkyl peroxides such as t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene T-butylperoxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, 2,5-dimethyl- 2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) ) Peroxyesters such as hexyne-3, diacyl peroxides such as 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, Organic peroxides such as hydroperoxides such as diisopropylbenzene hydroperoxide and 2,5-dimethyl-2,5-di (hydroperoxy) hexane, and ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide Or 2,2′-azobisisobutyronitrile, 2,2′-azobis (isobutyramide) dihalide, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], Azodi-t-butane, etc. Azo compounds, and the like.
上記溶融グラフト法においては、一軸又は二軸押出機等の混練機、横型二軸多円板装置等の横型二軸攪拌機、ダブルヘリカルリボン攪拌機等の縦型攪拌機等を用いて、前記エチレン系重合体と、該エチレン系重合体１００重量部に対して、前記エチレン性不飽和単量体を通常０．００５〜２０重量部、好ましくは０．１〜５重量部と、前記ラジカル発生剤を通常０．００１〜１０重量部、好ましくは０．０１〜５重量部とを、通常１００〜３００℃程度、好ましくは１００〜２００℃程度の温度下で前記オレフィン系重合体を溶融させて、通常０．５〜１０分間程度の時間でグラフト反応を実施する。 In the melt grafting method, the ethylene-based weight is used by using a kneader such as a uniaxial or biaxial extruder, a horizontal biaxial agitator such as a horizontal biaxial multi-disc apparatus, a vertical agitator such as a double helical ribbon agitator, or the like. The ethylenically unsaturated monomer is usually 0.005 to 20 parts by weight, preferably 0.1 to 5 parts by weight, and the radical generator is usually used with respect to 100 parts by weight of the polymer and the ethylene polymer. 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, is usually about 100 to 300 ° C., preferably about 100 to 200 ° C. .The grafting reaction is carried out for about 5 to 10 minutes.
本発明の極性基含有ポリエチレンの密度は、ＪＩＳ Ｋ６９２２−１及び２：１９９７に準じて測定されるものであり、０．９４０〜０．９７０ｇ／ｃｍ３、好ましくは０．９４５〜０．９６５ｇ／ｃｍ３、更に好ましくは０．９５０〜０．９６２ｇ／ｃｍ３である。密度が０．９４０ｇ／ｃｍ３未満では成形体の剛性が低下する傾向があり、また、ガスバリア性が低い、０．９７０ｇ／ｃｍ３を超えると成形体の耐久性が低下する傾向がある。
極性基含有ポリエチレンの密度は、極性基含有ポリエチレンの主体となるエチレン系重合体の密度を調整することにより制御することが可能であり、該エチレン系重合体の密度は、エチレンと共重合させるコモノマーの種類や量により変化させることにより、所望のものを得ることができる。
The density of the polar group-containing polyethylene of the present invention is measured according to JIS K6922-1 and 2: 1997, and is 0.940 to 0.970 g / cm 3 , preferably 0.945 to 0.965 g / cm 3 , more preferably 0.950 to 0.962 g / cm 3 . When the density is less than 0.940 g / cm 3 , the rigidity of the molded body tends to be lowered, and when the density is lower than 0.970 g / cm 3 , the durability of the molded body tends to be lowered.
The density of the polar group-containing polyethylene can be controlled by adjusting the density of the ethylene polymer that is the main component of the polar group-containing polyethylene. The density of the ethylene polymer is a comonomer that is copolymerized with ethylene. The desired product can be obtained by changing the type and amount.
本発明の極性基含有ポリエチレンのメルトフローレート（ＭＦＲ）は、ＪＩＳ Ｋ６９２２−２：１９９７に準拠して、温度１９０℃、荷重２．１６ｋｇにて測定されるものであり、１〜４０ｇ／１０分、好ましくは２〜３８ｇ／１０分、更に好ましくは３〜３５ｇ／１０分である。ＭＦＲが１ｇ／１０分未満では成形材料の流動性が低下して成形性が劣り、４０ｇ／１０分を超えると成形体の耐衝撃性が低下する。
極性基含有ポリエチレンのＭＦＲは、極性基含有ポリエチレンの主体となるエチレン系重合体のＭＦＲを調整することにより制御することが可能であり、該エチレン系重合体のＭＦＲは、エチレン重合温度や連鎖移動剤の使用等により調整することができ、所望のものを得ることができる。即ち、エチレンとα−オレフィンとの重合温度を上げることにより分子量を下げて、結果としてＭＦＲを大きくすることができ、重合温度を下げることにより分子量を上げて、結果としてＭＦＲを小さくすることができる。また、エチレンとα−オレフィンとの共重合反応において共存させる水素量（連鎖移動剤量）を増加させることにより分子量を下げて、結果としてＭＦＲを大きくすることができ、共存させる水素量（連鎖移動剤量）を減少させることにより分子量を上げて、結果としてＭＦＲを小さくすることができる。
The melt flow rate (MFR) of the polar group-containing polyethylene of the present invention is measured at a temperature of 190 ° C. and a load of 2.16 kg according to JIS K6922-2: 1997, and is 1 to 40 g / 10 min. The amount is preferably 2 to 38 g / 10 minutes, more preferably 3 to 35 g / 10 minutes. When the MFR is less than 1 g / 10 minutes, the fluidity of the molding material is lowered and the moldability is inferior, and when it exceeds 40 g / 10 minutes, the impact resistance of the molded article is lowered.
The MFR of the polar group-containing polyethylene can be controlled by adjusting the MFR of the ethylene polymer that is the main component of the polar group-containing polyethylene. The MFR of the ethylene polymer can be controlled by the ethylene polymerization temperature or chain transfer. It can be adjusted by the use of the agent and the desired product can be obtained. That is, by increasing the polymerization temperature of ethylene and α-olefin, the molecular weight can be decreased, and as a result, the MFR can be increased. By decreasing the polymerization temperature, the molecular weight can be increased, and as a result, the MFR can be decreased. . In addition, the molecular weight can be lowered by increasing the amount of hydrogen coexisting in the copolymerization reaction of ethylene and α-olefin (chain transfer agent amount), resulting in an increase in MFR, and the amount of hydrogen coexisting (chain transfer). The molecular weight can be increased by decreasing the (drug amount), and as a result, the MFR can be reduced.
３．有機化層状珪酸塩（Ａ）と極性基含有ポリエチレン（Ｂ）の両成分の割合
本発明のポリエチレン系積層用材料において、有機化層状珪酸塩（Ａ）と、極性基含有ポリエチレン（Ｂ）とからなるポリエチレン系積層用材料の両成分の割合は、有機化層状珪酸塩（Ａ）が５〜３０重量％、極性基含有ポリエチレン（Ｂ）が７０〜９５重量％、好ましくは有機化層状珪酸塩（Ａ）が８〜２０重量％、極性基含有ポリエチレン（Ｂ）が８０〜９２重量％である。有機化層状珪酸塩（Ａ）が５重量％未満では（極性基含有ポリエチレン（Ｂ）が９５重量％を超えると）ガスバリア性が低下し、またヘイズが低下せず透明性が不良となる場合があり、有機化層状珪酸塩（Ａ）が３０重量％を超え、極性基含有ポリエチレン（Ｂ）が７０重量％未満であると、流動性が低下して良好な成形体が得られず、また、衝撃強度が著しく低下する。
3. Ratio of both components of organic layered silicate (A) and polar group-containing polyethylene (B) In the polyethylene-based laminating material of the present invention, from organic layered silicate (A) and polar group-containing polyethylene (B). The ratio of both components of the resulting polyethylene-based laminating material is 5-30 wt% for the organic layered silicate (A), 70-95 wt% for the polar group-containing polyethylene (B), preferably the organic layered silicate ( A) is 8 to 20% by weight, and the polar group-containing polyethylene (B) is 80 to 92% by weight. When the organic layered silicate (A) is less than 5% by weight (when the polar group-containing polyethylene (B) exceeds 95% by weight), the gas barrier property is lowered, and the haze is not lowered and the transparency may be poor. Yes, when the organically modified layered silicate (A) exceeds 30% by weight and the polar group-containing polyethylene (B) is less than 70% by weight, the fluidity decreases and a good molded article cannot be obtained. Impact strength is significantly reduced.
４．ポリエチレン系積層用材料の特性
（１）粘度比
本発明のポリエチレン系積層用材料は、キャピラリーレオメーターにてシリンダー温度１９０℃、１ｍｍφ長さ３０ｍｍＬ／Ｄ＝３０ 流入角９０度のキャピラリーを用いて、せん断速度４８ｓｅｃ−１で測定される粘度η４８（Ｐａ・ｓ）とせん断速度３１００ｓｅｃ−１で測定される粘度η３１００（Ｐａ・ｓ）の比（η４８／η３１００）が７〜３０、好ましくは１０〜２０であることが重要である。
当該比（η４８／η３１００）が７未満では、成形時又はリサイクル成形時、高速成形性が劣り、３０を超えると物性が著しく低下する。当該比を大きくするには、前記エチレン系重合体の分子量分布を拡げるか、層状珪酸塩の添加量を増やすことが挙げられる。エチレン系重合体の分子量分布を拡げるためには、分子量の異なる成分を混合するか多段重合したり、分子量分布を広く出来る触媒（チーグラー触媒、好ましくはフィリップス触媒）を用いて重合すること等により達成することが出来る。
4). Properties of Polyethylene Laminating Material (1) Viscosity Ratio The polyethylene laminating material of the present invention is a capillary rheometer using a capillary with a cylinder temperature of 190 ° C., 1 mmφ length of 30 mm L / D = 30, an inflow angle of 90 degrees, the viscosity is measured at a shear rate of 48sec -1 η 48 (Pa · s ) and the ratio of the viscosity eta 3100 is measured at a shear rate 3100sec -1 (Pa · s) ( η 48 / η 3100) is 7-30, preferably Is important to be 10-20.
When the ratio (η 48 / η 3100 ) is less than 7, high-speed moldability is inferior at the time of molding or recycle molding, and when it exceeds 30, the physical properties are remarkably lowered. In order to increase the ratio, the molecular weight distribution of the ethylene polymer may be expanded or the amount of layered silicate added may be increased. In order to broaden the molecular weight distribution of ethylene polymers, it is achieved by mixing components with different molecular weights or performing multi-stage polymerization, or polymerizing using a catalyst that can broaden the molecular weight distribution (Ziegler catalyst, preferably Philips catalyst). I can do it.
（２）酸素透過係数
本発明のポリエチレン系積層用材料は、成形した１ｍｍの射出成形試験片を用いて測定したその酸素透過係数Ｐ（ｃｍ３・ｍｍ／ｍ２・２４ｈｒ・ａｔｍ）（２３℃・６５％ＲＨ）と、ポリエチレン系積層用材料の主成分である極性基含有ポリエチレン（Ｂ）の酸素透過係数Ｐ０（ｃｍ３・ｍｍ／ｍ２・２４ｈｒ・ａｔｍ）（２３℃・６５％ＲＨ）の比Ｐ／Ｐ０が０．７以下、好ましくは０．５以下であることが、ガスバリア性が優れるために好適である。Ｐ／Ｐ０を小さくするには、層状珪酸塩の量を増やすか、層状珪酸塩単体のアスペクト比（層状珪酸塩粒子の平均厚みと平均長さの比：長さ／厚み）を大きくすることで達成することが出来る。
(2) Oxygen Permeability Coefficient The polyethylene-based lamination material of the present invention has an oxygen permeability coefficient P (cm 3 · mm / m 2 · 24 hr · atm) (23 ° C.) measured using a molded 1 mm injection-molded test piece.・ 65% RH) and oxygen permeability coefficient P 0 (cm 3 · mm / m 2 · 24 hr · atm) (23 ° C. · 65% RH) of the polar group-containing polyethylene (B) which is the main component of the polyethylene-based laminating material ) Ratio P / P 0 is 0.7 or less, preferably 0.5 or less, because the gas barrier properties are excellent. To reduce the P / P 0, increase the amount of the layered silicate, the aspect ratio of the layered silicate alone (average thickness and the average length ratio of the layered silicate particles: length / thickness) is greater that Can be achieved.
（３）曲げ弾性率
本発明のポリエチレン系積層用材料は、その曲げ弾性率が９００ＭＰａ以上、好ましくは１０００〜３０００ＭＰａ、さらに好ましくは１０００〜２０００ＭＰａである。曲げ弾性率は、射出成形にてＪＩＳ Ｋ−７１５２−１：１９９９のタイプＡ金型にて２１０℃で成形して１０×８０×４ｍｍの試験片を作成し、ＪＩＳ Ｋ６９２２−２：２００５に準拠して測定される。
曲げ弾性率が、９００ＭＰａ未満ではポリエチレン系積層用材料を用いて薄肉の成形体にした場合、剛性不足となる場合がある。曲げ弾性率は、極性基含有ポリエチレンの密度を変更するか、有機化層状珪酸塩の含有量・種類を変更することにより調整可能である。
(3) Flexural modulus The polyethylene-based laminating material of the present invention has a flexural modulus of 900 MPa or more, preferably 1000 to 3000 MPa, and more preferably 1000 to 2000 MPa. The bending elastic modulus is 10 × 80 × 4 mm test piece formed by injection molding at 210 ° C. with a JIS K-7152-1: 1999 type A mold, and conforms to JIS K6922-2: 2005. Measured.
If the flexural modulus is less than 900 MPa, rigidity may be insufficient when a thin molded body is formed using a polyethylene-based laminating material. The flexural modulus can be adjusted by changing the density of the polar group-containing polyethylene or changing the content / type of the organically modified layered silicate.
（４）ヘイズ
本発明のポリエチレン系積層用材料は、成形した１ｍｍの射出成形試験片を用いて、ＪＩＳ Ｋ−７３６１−：１９９７で測定したそのヘイズτ（％）が８０％以下であり、かつポリエチレン系積層用材料の主成分である極性基含有ポリエチレン（Ｂ）のヘイズτ０（％）との比τ／τ０が０．８以下であることが、透明性が優れているために好適である。τ／τ０を０．８以下とすることは、透明核剤を添加して通常得られるヘイズの低減効果よりも優れており、本発明による透明化効果は顕著なものである。
ヘイズを向上させるには、基材である極性基含有ポリエチレンの結晶相に出来るだけ多く、且つ均一に層状珪酸塩を挿入することで達成できる。そのため、結晶化度が高い極性基含有ポリエチレンほどその効果は大きく、有機化層状珪酸塩の含有量・種類を変更することにより調整可能である。
(4) Haze The polyethylene-based laminating material of the present invention has a haze τ (%) measured by JIS K-7361-: 1997 using a molded 1 mm injection-molded test piece, and is 80% or less, and It is preferable that the ratio τ / τ 0 of the polar group-containing polyethylene (B), which is the main component of the polyethylene-based laminating material, with the haze τ 0 (%) is 0.8 or less because of excellent transparency. It is. Setting τ / τ 0 to 0.8 or less is superior to the haze reduction effect that is usually obtained by adding a transparent nucleating agent, and the transparency effect of the present invention is remarkable.
The haze can be improved by inserting the layered silicate as much as possible into the crystalline phase of the polar group-containing polyethylene as a base material as uniformly as possible. Therefore, the polar group-containing polyethylene having a higher degree of crystallinity has a larger effect, and can be adjusted by changing the content and type of the organically modified layered silicate.
５．任意成分について
上記のポリエチレン系積層用材料は、有機化層状珪酸塩（Ａ）と極性基含有ポリエチレン（Ｂ）とを常法に従い、ペレタイザーやホモジナイザー等による機械的な溶融混合によりペレット化した後、各種成形機により成形を行って所望の積層用材料とすることができる。
その際、上記の材料には、常法に従い、他のオレフィン系重合体やゴム等のほか、酸化防止剤、紫外線吸収剤、光安定剤、滑剤、帯電防止剤、防曇剤、ブロッキング防止剤、加工助剤、着色顔料、パール顔料、光輝材、偏光パール顔料、架橋剤、発泡剤、中和剤、熱安定剤、結晶核剤、無機又は有機充填剤、難燃剤等の公知の添加剤を配合することができる。着色方法としてはベース樹脂に必要量添加したコンパウンドでも、高濃度添加したマスターバッチを後ブレンドしてもよい。
5. About optional components After the above polyethylene-based laminating material is pelletized by mechanical melt mixing with a pelletizer or a homogenizer, etc., according to a conventional method, the organic layered silicate (A) and the polar group-containing polyethylene (B), Molding can be performed with various molding machines to obtain a desired material for lamination.
At that time, in addition to other olefinic polymers and rubbers, the above-mentioned materials include, in addition to antioxidants, ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, antifogging agents, and antiblocking agents, in accordance with conventional methods. , Processing aids, coloring pigments, pearl pigments, glittering materials, polarizing pearl pigments, crosslinking agents, foaming agents, neutralizing agents, thermal stabilizers, crystal nucleating agents, inorganic or organic fillers, flame retardants and other known additives Can be blended. As a coloring method, a compound added in a necessary amount to the base resin or a master batch added at a high concentration may be post-blended.
添加剤として、例えば酸化防止剤（フェノール系、リン系、イオウ系）、滑剤、帯電防止剤、光安定剤、紫外線吸収剤等を１種又は２種以上適宜併用することができる。他の充填材としては、炭酸カルシウム、タルク、金属粉（アルミニウム、銅、鉄、鉛など）、珪石、珪藻土、アルミナ、石膏、硫酸バリウム、カーボンナノチューブ、グラファイト、カーボンブラック、酸化チタン、各種ウィスカー等が使用可能である。いずれの場合でも、上記成形材料に、必要に応じ各種添加剤を配合し、混練押出機、バンバリーミキサー等にて混練し、成形用材料とすることができる。 As additives, for example, antioxidants (phenolic, phosphorus-based, sulfur-based), lubricants, antistatic agents, light stabilizers, ultraviolet absorbers, and the like can be appropriately used in combination of one or more. Other fillers include calcium carbonate, talc, metal powder (aluminum, copper, iron, lead, etc.), silica, diatomaceous earth, alumina, gypsum, barium sulfate, carbon nanotubes, graphite, carbon black, titanium oxide, various whiskers, etc. Can be used. In any case, various additives can be blended with the molding material as necessary, and the mixture can be kneaded with a kneading extruder, a Banbury mixer, or the like to obtain a molding material.
本発明のポリエチレン系積層用材料の製造方法としては特に限定されず、例えば、極性基含有ポリエチレン及び層状珪酸塩の所定量を直接配合して混合する方法、極性基含有ポリエチレンに所定配合量以上の層状珪酸塩を配合し混合してマスターバッチを調整し、調整されたマスターバッチに所定配合量となるように極性基を含有しないポリエチレンを加えて希釈する、いわゆるマスターバッチ法等が挙げられる。 The method for producing the polyethylene-based laminating material of the present invention is not particularly limited. For example, a method in which a predetermined amount of polar group-containing polyethylene and layered silicate are directly blended and mixed, or a polar group-containing polyethylene having a predetermined blending amount or more. There is a so-called master batch method in which a layered silicate is blended and mixed to prepare a master batch, and polyethylene that does not contain a polar group is added to the adjusted master batch to dilute it to a predetermined blending amount.
６．ポリエチレン系積層体の成形方法
本発明のポリエチレン系積層体の成形方法は、特に限定されないが、特に射出成形が好ましい。通常の射出成形機を用いて成形体とすることができ、成形条件は、求める成形品の大きさ、形状によって適宜設定可能であるが、ポリエチレン系積層体の温度１６０〜２７０℃、射出速度２０〜１０００ｍｍ／秒の条件で成形することが好ましい。
本発明のポリエチレン系積層体を用いて射出成形体を成形すると、層状珪酸塩が極性基含有ポリエチレン中にほぼ均一分散するが、層状珪酸塩の各層が一方向に並んだ配列構造を形成し、ガス分子がマトリックス樹脂（極性基含有ポリエチレン）中を通過するパスが長くなり、優れたガスバリア性効果を発揮することができる。
なお、各層が一方向に並んだ配列構造を形成しない層状珪酸塩も一部存在するが、これらの層状珪酸塩もマトリックス樹脂中にほぼ均一に微分散しているため、成形体の機械的強度等の特性をバランスよく向上させることができる。また、均一にナノレベルで分散した層状珪酸塩はポリマーの結晶中に取り込まれ、結果として、結晶相の結晶化度を均一に下げる効果をもたらす。この効果により、透明性が格段に向上する。
6). Method for Molding Polyethylene Laminate The method for molding the polyethylene laminate of the present invention is not particularly limited, but injection molding is particularly preferred. A molded body can be formed using a normal injection molding machine, and the molding conditions can be appropriately set depending on the size and shape of the molded product to be obtained. The temperature of the polyethylene-based laminate is 160 to 270 ° C., and the injection speed is 20 It is preferable to mold at a condition of ˜1000 mm / sec.
When molding an injection molded article using the polyethylene-based laminate of the present invention, the layered silicate is almost uniformly dispersed in the polar group-containing polyethylene, but each layer of the layered silicate forms an array structure arranged in one direction, The path through which gas molecules pass through the matrix resin (polar group-containing polyethylene) becomes longer, and an excellent gas barrier effect can be exhibited.
In addition, there are some layered silicates that do not form an array structure in which each layer is aligned in one direction, but these layered silicates are also dispersed almost uniformly in the matrix resin, so the mechanical strength of the molded body Etc. can be improved in a well-balanced manner. Further, the layered silicate uniformly dispersed at the nano level is incorporated into the crystal of the polymer, and as a result, the crystallinity of the crystal phase is lowered uniformly. By this effect, the transparency is remarkably improved.
７．積層体
上記ポリエチレン系積層用材料に対して、基材を積層することにより本発明の積層体を製造することができる。基材としては、プラスチック、金属、紙、ガラス等の各種の物品が挙げられ、特に好ましくは、プラスチック、中でもポリオレフィン系材料が好適である。基材の形状は特に限定されないが、フィルム、シート、板状のものが好ましい。
本発明のポリエチレン系積層用材料は、透明性に優れるので、ポリエチレン系積層用材料を基材に積層した積層体において、例えば、基材表面に印刷された文字等を明確に判別できる等、優れた効果を発現する。また、ガスバリア性に優れているのみならず、成形性、成形品外観、特に透明性に優れるため、各種包装材料として好適に用いることができ、産業上の有用性は非常に高い。
本発明の積層体は、透明性に優れるため、酸素透過防止性に優れたガスバリア性インモールド容器、例えばカップやインモールドカップとして好適である。
7). Laminated body The laminated body of this invention can be manufactured by laminating | stacking a base material with respect to the said polyethylene-type lamination | stacking material. Examples of the substrate include various articles such as plastic, metal, paper, glass, and the like, and particularly preferably a plastic, especially a polyolefin-based material. Although the shape of a base material is not specifically limited, A film, a sheet | seat, and a plate-shaped thing are preferable.
Since the polyethylene-based laminating material of the present invention is excellent in transparency, in a laminate in which a polyethylene-based laminating material is laminated on a base material, for example, characters printed on the surface of the base material can be clearly distinguished, etc. To express the effect. In addition to being excellent in gas barrier properties, it is excellent in moldability, appearance of molded products, and in particular, transparency, so that it can be suitably used as various packaging materials, and its industrial utility is very high.
Since the laminate of the present invention is excellent in transparency, it is suitable as a gas barrier in-mold container excellent in oxygen permeation prevention property, such as a cup or an in-mold cup.
以下に実施例を挙げて、本発明を更に具体的に説明するが、本発明は、その要旨を超えない限り、これらの実施例に制約されるものではない。なお、実施例で用いた測定方法は以下の通りである。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. In addition, the measuring method used in the Example is as follows.
（１）密度：ＪＩＳ Ｋ６９２２−１及び２：１９９７に準じて測定した。
（２）メルトフローレート（ＭＦＲ）：ＪＩＳ Ｋ６９２２−２：１９９７に準拠して、温度１９０℃、荷重２．１６ｋｇにおいて測定した。
（３）粘度：ＩＮＴＥＳＣＯ社製インテスコ全自動キャピラリーレオメーターを用い、直径１ｍｍ、長さ３０ｍｍ、材料入射角９０°のキャピラリーを使用して、設定温度１９０℃にて、せん断速度４８ｓｅｃ−１、せん断速度３１００ｓｅｃ−１の各せん断速度における粘度η（Ｐａ・ｓ）を測定した。
（４）成形体の酸素透過係数：東芝機械社製射出成形機ＩＳ−１５０を用い、設定温度２１０℃、射出速度５０ｍｍ／秒、射出保圧時間１０秒、金型温度４０℃、冷却時間２０秒の条件で、縦１２ｃｍ、横１２ｃｍ、厚さ１ｍｍのシートを作成した。ＭＯＣＯＮ社製ＯＸＴＲＡＮ２／２１を用い、湿度６５％ＲＨ、温度２３℃の条件で、上記方法で成形したサンプルシートの酸素透過係数（ｃｍ３・ｍｍ／ｍ２・２４ｈｒ・ａｔｍ）を測定した。
（５）曲げ弾性率：射出成形にてＪＩＳ Ｋ−７１５２−１：１９９９のタイプＡ金型にて２１０℃で成形して１０×８０×４ｍｍの試験片を作成し、ＪＩＳ Ｋ６９２２−２：２００５に準拠して測定した。
（６）シャルピー衝撃強度：ＪＩＳ Ｋ６９２２−２：２００５に準拠して測定した。４ＫＪ／ｍ２以上を「良好」とした。
（７）引張り衝撃強度：ＪＩＳ Ｋ６９２２−２：２００５に準拠して測定した。
（８）スパイラルフロー（２１０℃）：東芝機械社製ＩＳ−８０を用い、設定温度２１０℃、射出圧力７５ＭＰａ、射出時間５秒、冷却時間１０秒、保圧切替え位置７ｍｍ、クッション位置１．９〜２．１ｍｍ、金型温度３０℃の条件で、幅１０ｍｍ、厚み２ｍｍ、最長流路長２０００ｍｍのスパイラル流路を有する金型を用い、最長流動長を測定した。
（９）成形体表面の外観：射出成形品の外観を目視判定により、その状態を評価し、ムラがなく層状珪酸塩凝集が見られないもの又はそれに近いものを「良好」、明らかに層状珪酸塩の分散が悪く凝集が見られるものを「不良」とした。
（１０）ヘイズ：ＪＩＳ Ｋ７３６１−１：１９９７に準拠し、スガ試験機社製 直読ヘイズコンピューターを用いて測定した。サンプルは上記の酸素透過係数を測定したものと同条件で作成された厚さ１ｍｍの射出シートを用いた。
(1) Density: Measured according to JIS K6922-1 and 2: 1997.
(2) Melt flow rate (MFR): Measured at a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K6922-2: 1997.
(3) Viscosity: Using an INTESCO fully automatic capillary rheometer manufactured by INTESCO, using a capillary with a diameter of 1 mm, a length of 30 mm, and a material incident angle of 90 °, at a set temperature of 190 ° C., a shear rate of 48 sec −1 , shear The viscosity η (Pa · s) at each shear rate at a speed of 3100 sec −1 was measured.
(4) Oxygen permeability coefficient of molded article: using Toshiba Machine's injection molding machine IS-150, set temperature 210 ° C., injection speed 50 mm / second, injection holding time 10 seconds, mold temperature 40 ° C., cooling time 20 A sheet having a length of 12 cm, a width of 12 cm, and a thickness of 1 mm was prepared under the conditions of seconds. The oxygen transmission coefficient (cm 3 · mm / m 2 · 24 hr · atm) of the sample sheet molded by the above method was measured using MOCON OXTRAN 2/21 under conditions of a humidity of 65% RH and a temperature of 23 ° C.
(5) Flexural modulus: 10 × 80 × 4 mm test piece was formed by injection molding at 210 ° C. using a JIS K-7152-1: 1999 type A mold, and JIS K6922-2: 2005. Measured according to
(6) Charpy impact strength: measured according to JIS K6922-2: 2005. 4 KJ / m 2 or more was defined as “good”.
(7) Tensile impact strength: measured in accordance with JIS K6922-2: 2005.
(8) Spiral flow (210 ° C): using IS-80 manufactured by Toshiba Machine Co., Ltd., set temperature 210 ° C, injection pressure 75 MPa, injection time 5 seconds, cooling time 10 seconds, holding pressure switching position 7 mm, cushion position 1.9 The longest flow length was measured using a mold having a spiral flow path having a width of 10 mm, a thickness of 2 mm, and a longest flow path length of 2000 mm under conditions of ˜2.1 mm and a mold temperature of 30 ° C.
(9) Appearance of the surface of the molded product: The appearance of the injection-molded product is evaluated by visual judgment, and the state thereof is evaluated. A case where the salt was poorly dispersed and agglomeration was observed was defined as “bad”.
(10) Haze: Measured using a direct reading haze computer manufactured by Suga Test Instruments Co., Ltd. according to JIS K7361-1: 1997. The sample used was an injection sheet having a thickness of 1 mm prepared under the same conditions as those measured for the oxygen permeability coefficient.
１．有機化層状珪酸塩
（１）有機化モンモリロナイト
ＳＯＵＴＨＥＲＮ ＣＬＡＹ ＰＲＯＤＵＣＴＳ，ＩＮＣ社製Ｃｌｏｉｓｉｔｅ（登録商標）１５Ａ（ジメチルジタローアンモニウムクロリド処理有機化モンモリロナイト。有機物量：約４３％）
（２）有機化マイカ
コープケミカル社製ソマシフＭＡＥ（Ｃ１４〜Ｃ１８のジアルキルジメチルアンモニウム塩処理フッ素化マイカ。有機物量：約３７％）
（３）タルク
富士タルク工業社製ＬＭＳ−１００
２．造核剤
（４）旭電化社製ＮＡ−１１（環状有機リン酸エステル塩基多価金属塩）
1. Organized layered silicate (1) Organized montmorillonite SOUTHERN PLAY PRODUCTS, INC. Cloisite (registered trademark) 15A (treated with dimethyl ditallow ammonium chloride, treated montmorillonite. Organic content: about 43%)
(2) Organic mica OP Chemical Co. Somashif MAE (C 14 -C 18 dialkyl dimethyl ammonium salts fluorination treatment Mica organic matter:. 37%)
(3) Talc Fuji Talc Kogyo LMS-100
2. Nucleator (4) NA-11 manufactured by Asahi Denka Co. (cyclic organophosphate base polyvalent metal salt)
３．極性基含有ポリエチレン
（１）密度が０．９６２ｇ／ｃｍ３、ＭＦＲが５ｇ／１０分、無水マレイン酸化率が０．２３重量％の極性基含有ポリエチレン。
（２）密度が０．９６１ｇ／ｃｍ３、ＭＦＲが３４ｇ／１０分、無水マレイン酸化率が０．４３重量％の極性基含有ポリエチレン。
（３）密度が０．９５１ｇ／ｃｍ３、ＭＦＲが１０ｇ／１０分、無水マレイン酸化率が０．２８重量％の極性基含有ポリエチレン。
（４）密度が０．９２５ｇ／ｃｍ３、ＭＦＲが３ｇ／１０分、無水マレイン酸化率が０．４８重量％の極性基含有ポリエチレン。
（５）密度が０．９６２ｇ／ｃｍ３、ＭＦＲが０．５ｇ／１０分、無水マレイン酸化率が０．２３重量％の極性基含有ポリエチレン。
3. Polar group-containing polyethylene (1) A polar group-containing polyethylene having a density of 0.962 g / cm 3 , an MFR of 5 g / 10 min, and an anhydrous maleic acid oxidation rate of 0.23% by weight.
(2) A polar group-containing polyethylene having a density of 0.961 g / cm 3 , an MFR of 34 g / 10 min, and an anhydrous maleic acid oxidation rate of 0.43% by weight.
(3) Polar group-containing polyethylene having a density of 0.951 g / cm 3 , an MFR of 10 g / 10 min, and an anhydrous maleic acid oxidation rate of 0.28 wt%.
(4) A polar group-containing polyethylene having a density of 0.925 g / cm 3 , an MFR of 3 g / 10 min, and an anhydrous maleic acid oxidation rate of 0.48 wt%.
(5) A polar group-containing polyethylene having a density of 0.962 g / cm 3 , an MFR of 0.5 g / 10 min, and an anhydrous maleic acid oxidation rate of 0.23% by weight.
［実施例１］
日本製鋼所社製二軸押出機ＴＥＸ３０α中に、有機化マイカ（コープケミカル社製ソマシフＭＡＥ）１５重量％、極性基含有ポリエチレン（１）８５重量％をフィードし、設定温度２１０℃にて溶融混練し、押出したストランドをペレタイザーによりペレット化した。得られたペレットを使用し、東芝機械社製射出成形機ＩＳ−１５０を用い、設定温度２１０℃、射出速度５０ｍｍ／秒、射出時間１０秒、金型温度４０℃、冷却時間２０秒の条件で、縦１２ｃｍ、横１２ｃｍ、厚さ１ｍｍのシートを作成した。得られたシートを用いて酸素透過係数Ｐ及びヘイズτを測定した。
また、極性基含有ポリエチレン（１）のみから同様に厚さ１ｍｍのシートを作成し、得られたシートを用いて酸素透過係数Ｐ０及びヘイズτ０を測定した。これらからＰ／Ｐ０、τ／τ０を求めた。
更に、上記により得られたペレットについて、各種物性測定結果を表１に示した。
[Example 1]
15% by weight of organic mica (Somasif MAE manufactured by Corp Chemical Co.) and 85% by weight of polar group-containing polyethylene (1) are fed into a twin screw extruder TEX30α manufactured by Nippon Steel Works, and melt-kneaded at a set temperature of 210 ° C. The extruded strand was pelletized with a pelletizer. Using the obtained pellets, using an injection molding machine IS-150 manufactured by Toshiba Machine Co., Ltd. under the conditions of a set temperature of 210 ° C., an injection speed of 50 mm / second, an injection time of 10 seconds, a mold temperature of 40 ° C., and a cooling time of 20 seconds. A sheet having a length of 12 cm, a width of 12 cm, and a thickness of 1 mm was prepared. The oxygen permeability coefficient P and haze τ were measured using the obtained sheet.
In addition, a sheet having a similarly thick 1mm only polar group-containing polyethylene (1), the oxygen permeability coefficient P 0 and haze tau 0 Using the obtained sheet was measured. From these, P / P 0 and τ / τ 0 were obtained.
Furthermore, various physical property measurement results of the pellets obtained as described above are shown in Table 1.
［実施例２］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）の代わりに有機化モンモリロナイト（ＳＯＵＴＨＥＲＮ ＣＬＡＹ ＰＲＯＤＵＣＴＳ，ＩＮＣ社製Ｃｌｏｉｓｉｔｅ（登録商標）１５Ａ）を使用し、配合割合を１５重量％から１０重量％にし、極性基含有ポリエチレン（１）の配合割合を９０重量％とした以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。
[Example 2]
Organized montmorillonite (SOUTHERN PLAY PRODUCTS, INC. Cloisite (registered trademark) 15A) was used in place of organic mica (Corpus Chemicals Somasifu MAE), and the blending ratio was changed from 15 wt% to 10 wt%. The same procedure as in Example 1 was conducted except that the blending ratio of the polyethylene (1) contained was 90% by weight.
Table 1 shows the results of measuring various physical properties.
［実施例３］
極性基含有ポリエチレン（１）の代わりに極性基含有ポリエチレン（２）を使用した以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。
[Example 3]
It carried out like Example 1 except having used polar group content polyethylene (2) instead of polar group content polyethylene (1).
Table 1 shows the results of measuring various physical properties.
［実施例４］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）の配合割合を１５重量％から１０重量％にし、極性基含有ポリエチレン（１）の代わりに極性基含有ポリエチレン（３）を使用し、配合割合を９０重量％にした以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。
[Example 4]
Organized mica (Somasif MAE manufactured by Co-op Chemical Co., Ltd.) was blended in a proportion of 15 to 10% by weight, and polar group-containing polyethylene (3) was used instead of polar group-containing polyethylene (1), and the blending ratio was 90 wt. The same procedure as in Example 1 was performed except that the content was changed to%.
Table 1 shows the results of measuring various physical properties.
［実施例５］
極性基含有ポリエチレン（１）の代わりに極性基含有ポリエチレン（３）を使用した以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。
[Example 5]
It carried out like Example 1 except having used polar group content polyethylene (3) instead of polar group content polyethylene (1).
Table 1 shows the results of measuring various physical properties.
［比較例１］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）を使用しないこと以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体のガスバリア性が低く、ヘイズも低かった。
[Comparative Example 1]
The same procedure as in Example 1 was performed except that organic mica (Somasif MAE manufactured by Corp Chemical Co.) was not used.
Table 1 shows the results of measuring various physical properties. In this example, the molded article had low gas barrier properties and low haze.
［比較例２］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）を使用しないこと以外は実施例４と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体のガスバリア性が低く、ヘイズも低かった。
[Comparative Example 2]
The same operation as in Example 4 was performed except that organic mica (Somasif MAE manufactured by Corp Chemical Co., Ltd.) was not used.
Table 1 shows the results of measuring various physical properties. In this example, the molded article had low gas barrier properties and low haze.
［比較例３］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）を使用しないこと以外は実施例３と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体のガスバリア性が低く、ヘイズも低かった。
[Comparative Example 3]
The same procedure as in Example 3 was performed except that organic mica (Somasif MAE manufactured by Corp Chemical Co., Ltd.) was not used.
Table 1 shows the results of measuring various physical properties. In this example, the molded article had low gas barrier properties and low haze.
［比較例４］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）の代わりにタルク（富士タルク工業社製ＬＭＳ−１００）を使用した以外は実施例２と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体のＰ／Ｐ０が大きく成形体のガスバリア性の改良効果が低く、ヘイズも低かった。
[Comparative Example 4]
The same procedure as in Example 2 was performed except that talc (LMS-100 manufactured by Fuji Talc Industrial Co., Ltd.) was used instead of organic mica (Somasif MAE manufactured by Corp Chemical Co.).
Table 1 shows the results of measuring various physical properties. In this example, the gas barrier effect of improving the P / P 0 is large molded body of the molded body is low, haze was also low.
［比較例５］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）を使用せず、旭電化社製造核剤ＮＡ−１１を０．１重量％添加した以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体のガスバリア性の改良効果が低く、ヘイズの改良効果も十分ではなかった。
[Comparative Example 5]
The same procedure as in Example 1 was carried out except that 0.1% by weight of Asahi Denka Co., Ltd. nucleating agent NA-11 was added without using organic mica (Somasif MAE manufactured by Corp Chemical Co., Ltd.).
Table 1 shows the results of measuring various physical properties. In this example, the effect of improving the gas barrier property of the molded article was low, and the effect of improving haze was not sufficient.
［比較例６］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）を使用せず、旭電化社製造核剤ＮＡ−１１を０．２重量％添加した以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体のガスバリア性の改良効果が低く、ヘイズの改良効果も十分ではなかった。
[Comparative Example 6]
The same procedure as in Example 1 was performed except that 0.2% by weight of Asahi Denka Co., Ltd. nucleating agent NA-11 was added without using organic mica (Somafif MAE manufactured by Corp Chemical Co., Ltd.).
Table 1 shows the results of measuring various physical properties. In this example, the effect of improving the gas barrier property of the molded article was low, and the effect of improving haze was not sufficient.
［比較例７］
有機化モンモリロナイト（ＳＯＵＴＨＥＲＮ ＣＬＡＹ ＰＲＯＤＵＣＴＳ，ＩＮＣ社製Ｃｌｏｉｓｉｔｅ（登録商標）１５Ａ）の配合割合を３５重量％とし、極性基含有ポリエチレン（１）の配合割合を６５重量％とした以外は実施例２と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体の外観が悪く、ヘイズの改良効果も低かった。
[Comparative Example 7]
Example 2 except that the blending ratio of organic montmorillonite (SOUTHERN PLAY PROCUTS, INC. Cloisite (registered trademark) 15A) was 35% by weight, and the polar group-containing polyethylene (1) was 65% by weight. I went to.
Table 1 shows the results of measuring various physical properties. In this example, the appearance of the molded body was poor and the effect of improving haze was low.
［比較例８］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）の配合割合を３５重量％とし、極性基含有ポリエチレン（１）の配合割合を６５重量％とした以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体の外観が悪く、ヘイズの改良効果も低かった。
[Comparative Example 8]
The same procedure as in Example 1 was carried out except that the blending ratio of organic mica (Somasif MAE manufactured by Corp Chemical Co., Ltd.) was 35% by weight and the blending ratio of the polar group-containing polyethylene (1) was 65% by weight.
Table 1 shows the results of measuring various physical properties. In this example, the appearance of the molded body was poor and the effect of improving haze was low.
［比較例９］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）の配合割合を３重量％とし、極性基含有ポリエチレン（１）の配合割合を９７重量％とした以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体のガスバリア性の改良効果が低く、ヘイズの改良効果も十分ではなかった。
[Comparative Example 9]
The same procedure as in Example 1 was carried out except that the blending ratio of organic mica (Somasif MAE manufactured by Corp Chemical Co., Ltd.) was 3% by weight and the blending ratio of the polar group-containing polyethylene (1) was 97% by weight.
Table 1 shows the results of measuring various physical properties. In this example, the effect of improving the gas barrier property of the molded article was low, and the effect of improving haze was not sufficient.
［比較例１０］
有機化マイカ（コープケミカル社製ソマシフＭＡＥ）を使用せず、極性基含有ポリエチレン（１）の代わりに極性基含有ポリエチレン（４）を使用した以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。成形体のガスバリア性の改良効果が低く、曲げ弾性率も低かった。
[Comparative Example 10]
The same procedure as in Example 1 was carried out except that organic mica (Somasif MAE manufactured by Coop Chemical Co., Ltd.) was not used and polar group-containing polyethylene (4) was used instead of polar group-containing polyethylene (1).
Table 1 shows the results of measuring various physical properties. The effect of improving the gas barrier property of the molded product was low, and the flexural modulus was also low.
［比較例１１］
極性基含有ポリエチレン（１）の代わりに極性基含有ポリエチレン（４）を使用した以外は実施例１と同様に行なった。
各種物性測定結果を表１に示した。この例では、成形体のガスバリア性の改良効果が低く、ヘイズの改良効果も十分ではなかった。
[Comparative Example 11]
It carried out like Example 1 except having used polar group content polyethylene (4) instead of polar group content polyethylene (1).
Table 1 shows the results of measuring various physical properties. In this example, the effect of improving the gas barrier property of the molded article was low, and the effect of improving haze was not sufficient.
［比較例１２］
極性基含有ポリエチレン（１）の代わりに極性基含有ポリエチレン（５）を使用した以外は実施例１と同様に行なった。
その結果、混練時に押出機のモータートルクの急激な上昇が起こったため、ペレットを得ることが出来なかった。
[Comparative Example 12]
It carried out like Example 1 except having used polar group content polyethylene (5) instead of polar group content polyethylene (1).
As a result, since the motor torque of the extruder suddenly increased during kneading, pellets could not be obtained.
［実施例６］
日本製鋼所社製二軸押出機ＴＥＸ３０α中に、有機化マイカ（コープケミカル社製ソマシフＭＡＥ）１５重量％、極性基含有ポリエチレン（１）８５重量％をフィードし、設定温度２１０℃にて溶融混練し、押出したストランドをペレタイザーによりペレット化した。
得られたペレットを使用し、東芝機械社製射出成形機ＩＳ−１５０を用い、設定温度２１０℃、射出速度５０ｍｍ／秒、射出時間１０秒、金型温度４５℃、冷却時間２０秒の条件で、上部開口部内径６３ｍｍ、底面部直径５１ｍｍ、高さ１０４ｍｍ、厚さ０．７ｍｍ、上部開口部周縁フランジ部の幅５ｍｍのカップ用金型を用いて、カップの胴部を囲む大きさのポリエチレンテレフタレートフィルムのラベル（表面に、１文字当たりの大きさが２ｍｍ×２ｍｍ四方の升目いっぱいに入るひらがな５０文字を印刷したもの）をセットし、内容積約２５０ｍｌのインモールドラベルカップを作成した。その結果、ラベルの文字は目視により明瞭に判読できた。
[Example 6]
15% by weight of organic mica (Somasif MAE manufactured by Corp Chemical Co.) and 85% by weight of polar group-containing polyethylene (1) are fed into a twin screw extruder TEX30α manufactured by Nippon Steel Works, and melt-kneaded at a set temperature of 210 ° C. The extruded strand was pelletized with a pelletizer.
Using the obtained pellets, using an injection molding machine IS-150 manufactured by Toshiba Machine Co., Ltd. under the conditions of a set temperature of 210 ° C., an injection speed of 50 mm / second, an injection time of 10 seconds, a mold temperature of 45 ° C., and a cooling time of 20 seconds. Polyethylene of a size that surrounds the body of the cup using a cup mold with an inner diameter of the upper opening of 63 mm, a bottom diameter of 51 mm, a height of 104 mm, a thickness of 0.7 mm, and a peripheral flange flange of the upper opening of 5 mm. A label of terephthalate film (printed with 50 characters of hiragana that fills a square of 2 mm × 2 mm square per character) was set on the surface, and an in-mold label cup with an internal volume of about 250 ml was prepared. As a result, the characters on the label could be clearly read by visual inspection.
［比較例１３］
有機化マイカを使用しないこと以外は、実施例６と同様に行なった。しかし、樹脂の流動性が悪く、内容積約２５０ｍｌのカップを作成することができなかった。
[Comparative Example 13]
The same procedure as in Example 6 was performed except that organic mica was not used. However, the fluidity of the resin was poor, making it impossible to make a cup with an internal volume of about 250 ml.
表１の評価結果から明らかなように、本発明の実施例１〜５の成形体は、特定の成形材料を採用することにより、バリア性を有し、かつ高流動性を現出させることができ、成形性に優れたバリア性、透明性を呈する成形体であることがわかる。すなわち、バリア性、透明性（ヘイズ）が良好であり、適度な流動性能を有し、成形体の物性に著しい低下がなく、成形性が良好であることがわかる。
一方、比較例１〜１２の成形体は、バリア性、成形性、成形体の物性のいずれかの一つ以上の性能評価が悪い結果となっていることがわかる。
As is apparent from the evaluation results of Table 1, the molded bodies of Examples 1 to 5 of the present invention have a barrier property and can exhibit high fluidity by adopting a specific molding material. It can be seen that the molded product exhibits excellent barrier properties and transparency. That is, it can be seen that the barrier properties and transparency (haze) are good, the fluidity is appropriate, the physical properties of the molded article are not significantly reduced, and the moldability is good.
On the other hand, it can be seen that the molded bodies of Comparative Examples 1 to 12 have a poor result of performance evaluation of one or more of barrier properties, moldability, and physical properties of the molded bodies.
本発明によれば、ガスバリア性、特に酸素透過防止性に優れるばかりでなく、成形性、成形品外観、機械的強度、透明性、特にヘイズに優れたポリエチレン系積層用材料及びその積層体を得ることができ、その特性によりガスバリア性インモールド容器、例えばカップやインモールドカップなど各種包装容器分野をはじめ広範囲の分野で利用できる。 According to the present invention, it is possible to obtain a polyethylene-based laminating material and a laminate thereof that not only have excellent gas barrier properties, particularly oxygen permeation-preventing properties, but also have excellent moldability, appearance of molded products, mechanical strength, transparency, and particularly haze. It can be used in a wide range of fields including various types of packaging containers such as gas barrier in-mold containers such as cups and in-mold cups.
Claims (5)
極性基含有ポリエチレン（Ｂ）は、前駆体としての極性基を含まないエチレン系重合体に極性基としてカルボン酸無水物基を有するエチレン性不飽和単量体をグラフト反応させた重合体、又はこれに極性基を含まないエチレン系重合体をブレンドした重合体であり、かつ下記の特性（１）〜（４）を満足することを特徴とするポリエチレン系積層用材料。
特性（１）：キャピラリーレオメーターにて温度１９０℃、せん断速度４８ｓｅｃ−１で測定される粘度η４８（Ｐａ・ｓ）とせん断速度３１００ｓｅｃ−１で測定される粘度η３１００（Ｐａ・ｓ）の比（η４８／η３１００）が７〜３０である。
特性（２）：ポリエチレン系積層用材料を成形したときの酸素透過係数Ｐ（ｃｍ３・ｍｍ／ｍ２・２４ｈｒ・ａｔｍ）（２３℃・６５％ＲＨ）と、ポリエチレン系積層用材料の主成分である極性基含有ポリエチレン（Ｂ）の酸素透過係数Ｐ０（ｃｍ３・ｍｍ／ｍ２・２４ｈｒ・ａｔｍ）（２３℃・６５％ＲＨ）の比Ｐ／Ｐ０が０．７以下である。
特性（３）：成形したときの曲げ弾性率が９００ＭＰａ以上である。
特性（４）：ポリエチレン系積層用材料を成形したときのヘイズτ（％）が８０％以下であり、かつポリエチレン系積層用材料の主成分である極性基含有ポリエチレン（Ｂ）のヘイズτ０（％）との比τ／τ０が０．８以下である。 An organic layered silicate (A) of 5 to 30% by weight, a density of 0.940 to 0.970 g / cm 3 , a temperature of 190 ° C., a melt flow rate (MFR) measured at a load of 2.16 kg of 3 to 3 A polyethylene-based laminating material comprising 70 to 95% by weight of a polar group-containing polyethylene (B) that is 35 g / 10 min,
The polar group-containing polyethylene (B) is a polymer obtained by graft-reacting an ethylenically unsaturated monomer having a carboxylic acid anhydride group as a polar group to an ethylene polymer that does not contain a polar group as a precursor, or this A polyethylene-based laminating material characterized in that it is a polymer obtained by blending an ethylene-based polymer containing no polar group and satisfies the following characteristics (1) to (4).
Characteristic (1): Viscosity η 48 (Pa · s) measured at a temperature of 190 ° C. and a shear rate of 48 sec −1 with a capillary rheometer and a viscosity η 3100 (Pa · s) measured at a shear rate of 3100 sec −1 The ratio (η 48 / η 3100 ) is 7-30.
Characteristic (2): Oxygen transmission coefficient P (cm 3 · mm / m 2 · 24 hr · atm) (23 ° C. · 65% RH) when a polyethylene laminate material is molded, and main components of the polyethylene laminate material The ratio P / P 0 of the oxygen permeability coefficient P 0 (cm 3 · mm / m 2 · 24 hr · atm) (23 ° C. · 65% RH) of the polar group-containing polyethylene (B) is 0.7 or less.
Characteristic (3): The bending elastic modulus when molded is 900 MPa or more.
Characteristic (4): Haze τ (%) when the polyethylene-based laminating material is molded is 80% or less, and haze τ 0 of the polar group-containing polyethylene (B) which is the main component of the polyethylene-based laminating material. %) And the ratio τ / τ 0 is 0.8 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008278175A JP5156578B2 (en) | 2008-10-29 | 2008-10-29 | Polyethylene-based laminating material and laminated body thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008278175A JP5156578B2 (en) | 2008-10-29 | 2008-10-29 | Polyethylene-based laminating material and laminated body thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010106114A JP2010106114A (en) | 2010-05-13 |
| JP5156578B2 true JP5156578B2 (en) | 2013-03-06 |
Family
ID=42295890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008278175A Active JP5156578B2 (en) | 2008-10-29 | 2008-10-29 | Polyethylene-based laminating material and laminated body thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5156578B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7458178B2 (en) | 2019-12-13 | 2024-03-29 | 株式会社ブリヂストン | drain pipe structure |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3269277B2 (en) * | 1994-04-15 | 2002-03-25 | 三菱化学株式会社 | Thermoplastic resin composition |
| JP2000129056A (en) * | 1998-10-21 | 2000-05-09 | Showa Denko Kk | Adhesive resin composite and its layered product |
| AUPS146402A0 (en) * | 2002-03-28 | 2002-05-09 | Compco Pty Ltd | Nanofiller compositions |
| FR2854899B1 (en) * | 2003-05-16 | 2006-07-07 | Atofina | COMPOSITIONS OF OLEFINIC THERMOPLASTIC POLYMERS AND NANOMETRIC SIZE LOADS IN THE FORM OF MIXTURES |
-
2008
- 2008-10-29 JP JP2008278175A patent/JP5156578B2/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7458178B2 (en) | 2019-12-13 | 2024-03-29 | 株式会社ブリヂストン | drain pipe structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010106114A (en) | 2010-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7037970B2 (en) | Process for increasing the melt strength of ethylene-vinyl carboxylate copolymers | |
| EP1896539B1 (en) | Filled tpo compositions, methods of making the same, and articles prepared from the same | |
| US6583209B2 (en) | Propylene polymer composites having improved melt strength | |
| US6861481B2 (en) | Ionomeric nanocomposites and articles therefrom | |
| AU2009202782B8 (en) | Methods, compositions and blends for forming articles having improved environmental stress crack resistance | |
| WO2009092420A1 (en) | Thermoplastic elastomer compositions | |
| JP5232504B2 (en) | Polyethylene container lid | |
| JP5156578B2 (en) | Polyethylene-based laminating material and laminated body thereof | |
| JP5806626B2 (en) | Polypropylene resin composition containing glass fine particle hollow sphere powder and injection molded product thereof | |
| JP5156530B2 (en) | Polyethylene molding material and molded body thereof | |
| AU2004224049A1 (en) | Polyolefin nanocomposite compositions | |
| JP5124419B2 (en) | Polyethylene container | |
| EP1408077A1 (en) | Polymer composition comprising nanofillers | |
| JP2007106924A (en) | Resin composition and molded article thereof | |
| JP4258959B2 (en) | Polypropylene resin composition and production method | |
| EP2083022A1 (en) | Method for producing syndiotactic propylene polymer | |
| EP4059969A1 (en) | Resin composition and molded article | |
| JP2000001579A (en) | Polyethylene resin composition | |
| JP2009114329A (en) | Polyethylene based resin composition and its use | |
| JP4899578B2 (en) | Modified olefin polymer composition and olefin polymer composition using the same | |
| WO2014059212A1 (en) | Articles prepared from nanofilled ionomer compositions | |
| JP4308347B2 (en) | Method for producing thermoplastic elastomer composition | |
| JP2010209225A (en) | Polypropylene resin molding | |
| JP2008222805A (en) | Polypropylene-based resin composition having excellent scratch resistance and molding method thereof | |
| Collar et al. | On chemical modified polyolefins by grafting of polar monomers: a survey based on recent patents literature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20101125 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120209 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120221 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120420 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121120 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121210 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151214 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5156578 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151214 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |